Corrosion inhibiting composition



United States Patent 3,453,124 CORROSION INHIBITING COMPOSITION RobertG. Wurstner, Parma Heights, Ohio, assignor to The Lubrizol Corporation,Wicklifie, Ohio, a corporation of Ohio No Drawing. Continuation-impartof application Ser. No. 300,691, Aug. 7, 1963. This application May 24,1967, Ser. No. 640,801

Int. Cl. 'C09k 3/18; C09d /08 US. Cl. 10614 16 Claims ABSTRACT OF THEDISCLOSURE This is a continuation-in-part of copending application Ser.No. 379,717, filed July 1, 1964 now abandoned, which in turn is acontinuation-in-part application of Ser. No. 300,691, filed Aug. 7,1963, now abandoned.

This invention relates to novel phosphorus-containing compositions andprocesses for their preparation. In a more particular sense, it relatesto corrosion-inhibiting coating compositions for metals comprising theaforesaid compositions.

The corrosion of metal surfaces is of obvious economic significance inmany industrial applications and, as a consequence, the inhibition ofsuch corrosion is a matter of prime consideration. It is of particularsignificance to users of steel and other ferrous alloys. The corrosionof such ferrous metal alloys is largely a matter of rust formation whichin turn involves the overall conversion of the free metal to its oxides.

The theory which best explains such oxidation of ferrous metal articlespostulates the essential presence of both water and oxygen. Even minutetraces of moisture are suflicient, according to this theory, to inducedissolution of iron therein and the formation of ferrous oxide until thewater becomes saturated with ferrous ions. The presence of oxygen causesoxidation of the resulting ferric hydroxide which settles out ofsolution and is ultimately converted to ferric oxide or rust.

The above sequence of reactions can be prevented, or at least in largemeasure inhibited, by relatively impermeable coatings which have theefiect of excluding moisture and/ or oxygen from contact with the metalsurface. Such coatings are often exposed to high humidity, corrosiveatmosphere, etc., and to the extent that these coatings are penetratedor otherwise harmed by such influences they become ineffective for thedesired purpose. It is also important that such coatings adhere tightlyto the metal surface and resist flaking, crazing, blistering, powdering,and other forms of loss of adhesion. A satisfactory corro sion-proofingcoating, then, must have the ability'to resist weathering, highhumidity, and corrosive atmospheres such as salt-laden mist or fogs, aircontaminated with industrial waste, road dirt, calcium chloride, etc.,so that the uniform protective film is maintained on all or most of themetal surface.

The corrosion of metal surfaces is of special economic significance tothe owners and manufacturers of automobiles. Every car owner is aware ofthe corrosion which starts on the inner or underside of automobilebodies such as inside the rocker panels, fender wells, headlightassemblies, and door panels. The corrosion rate is especially high incertain geographical areas which are subjected to severe weather duringthe winter months necessitating the use of sand, salt, calcium chloride,cinders, gravel, etc., to maintain the roads in useable condition. Insome cases it may only be a matter of a year or two before therelatively light gauge automotive body steel is completely converted toiron oxide. When this point is reached, the high quality exteriorfinishes flake off and reveal the metal destruction which has occurred.This inside-out corrosion destroys the appearance, the structuralreliability, and in all cases the monetary value of the vehicle.

Automobile producers have waged a constant battle against thisinside-out body corrosion. Mastics and sealers have been usedextensively as physical barriers to corrosive agents, and corrosioninhibiting primers have been used on underbody surfaces when they do notinterfere with production line welding techniques. When possible, zinccoated galvanized steel is used in substantial amounts to produce manybody components directly exposed to corrosive agents. These efforts andmany others by the automotive producers, however, have only reducedunderbody corrosion problems; the problems remain. The asphalt masticundercoatings failed to give the desired permanent protection againstcorrosion since on hardening due to age, these coatings crack and loseadhesion, especially when exposed to low ambient temperatures.

Corrosion inhibiting paints have also been utilized as underbodycoatings, but these are not particularly desirable because of the degreeof metal preparation required prior to their application which is eitherimpossible or impractical.

It is therefore an object of this invention to provide novelphosphorus-containing compositions and processes for their preparation.

It is also an object of this invention to provide corrosion-inhibitingcoating compositions for metals, especially ferrous metals.

It is also an object of this invention to provide novel coatingcompositions for metals, which compositions are resistant to weathering,abrasion, crazing, and undercutting.

It is further an object of this invention to providecorrosion-inhibiting coating compositions for metals, which compositionsmay be easily and inexpensively applied to said metal surfaces.

These and other objects are attained in accordance with this inventionby providing a composition prepared by the process which comprisesreacting of a temperature of at least about 25 C. up to thedecomposition temperature of the reactants of:

(A) from about 5 to about 10 parts by weight of a non- Newtoniancolloidal disperse system comprising (1) solid, metal-containingcolloidal particles selected from the class consisting of alkali andalkaline earth metal carbonates predispersed in (2) a dispersing medium,and (3) as an essential third component, at least one organic compoundwhich is soluble in said disperse medium, the molecules of said organiccompound being characterized by a hydrophobic portion and at least onepolar substituent, with (B) from about 1 to about 2 parts by weight ofan acidic ester of a phosphoric acid.

The product of this reaction is generally a grease-like material havinga consistency ranging from fluid to semisolid. The corrosion-inhibitingfilms of this invention may be applied to metal surfaces by any one ofthe ordinary methods such as brushing, spraying, dip-coating,flowcoating, roller-coating, and the like. The viscosity of thecorrosion-inhibiting composition may be adjusted for the particularmethod of application selected by adding a suitable amount of diluentsuch as the hydrocarbon and halo hydrocarbon solvents. Volatile ornon-volatile diluents can be used. Examples of such solvents include thealkanes having from five to fifteen carbon atoms, the aromatichydrocarbons having from six to thirty carbon atoms, the variouspetroleum distillates and the halo and polyhailo hydrocarbons havingfrom two to twenty carbon atoms. More specifically, examples of suchsolvents include n-hexane, n-pentane, isooctane, dodecane, benzene,xylene, aromatic petroleum spirits, mineral spirits, turpentine, 1,1,1trichloroethane, 1,1 dichlorobutane, 1,4-dichlorobutane, l-chlorohexane,chlorocyclohexane, etc. The metal surface which has been thus coated isdried either by exposure to air or by means of a baking procedure. Thecomposition-s may also be diluted with mineral oil or other non-volatileorganic liquids.

The non-Newtonian colloidal disperse systems The terminology dispersesystem as used in the specification and claims is a term of art genericto colloids or colloidal solutions, e.g., any homogeneous mediumcontaining dispersed entities of any size and state, B. Jirgensons andM. E. Straumanis, A Short Textbook on Colloidal Chemistry (2nd ed.), TheMacmillan Co., N.Y., 1962, page 1 thereof. However, the particulardisperse systems used as reactants in the present invention form asubgenus within this broad class of disperse systems, this subgenusbeing characterized by several important features.

This subgenus comprises those disperse systems wherein at least aportion of the particles dispersed therein are solid, metal-containingparticles formed in situ. At least about to about 50% are particles ofthis type and preferably, substantially all of said solid particles areformed in situ.

So long as the solid particles remain dispersed in the dispersing mediumas colloidal particles the particle size is not critical. Ordinarily,the particles will not exceed 5000 A. However, it is preferred that themaximum unit particle size be less than about 1000 A. In a particularlypreferred aspect of the invention, the unit particle size is less thanabout 400 A. Systems having a unit particle size in the range of 30 A to200 A give excellent results. The minimum unit particle size is at leastA and preferably at least about A.

The language unit particle size is intended to designate the averageparticle size of the solid, metal-containing particles assuming maximumdispersion of the individual particles throughout the disperse medium.That is, the unit particle is that particle which corresponds in size tothe average size of the metal-containing particles and is capable ofindependent existence within the disperse system as a discrete colloidalparticle. These metalcontaining particles are found in two forms in thedisperse systems. Individual unit particles can be dispersed as suchthroughout the medium or unit particles can form an agglomerate, incombination with other materials (e.g., another metal-containingparticle, the disperse medium, etc.) which are present in the dispersesystems. These agglomerates are dispersed through the system asmetalcontaining particles. Obviously, the particle size" of theagglomerate is substantially greater than the unit particle size.Furthermore, it is equally apparent that this agglomerate size issubject to wide variations, even within the same disperse system. Theagglomerate size varies, for example, with the degree of shearing actionemployed in dispersing the unit particles. That is, mechanical agitationof the disperse system tends to break down the agglomerates into theindividual components thereof and disperse these individual componentsthroughout the disperse medium. The ultimate in dispersion is achievedwhen each solid, metal-containing particle is individually dispersed inthe medium. Accordingly, the disperse systems are characterized withreference to the unit particle size, it being apparent to those skilledin the art that the unit particle size represents the average size ofsolid, metal-containing particles present in the system which can existindependently. The average particle size of the metal-containing solidparticles in the system can be made to approach the unit particle sizevalue by the application of a shearing action to the existent system orduring the formation of the disperse system as the particles are beingformed in situ. It is not necessary that maximum particle dispersionexist to have useful disperse systems. The agitation associated withhomogenization of the overbased material and conversion agent producessufficient particle dispersion.

The solid metal-containing colloidal particles are alkali or alkalineearth metal carbonates, hydrates thereof, or mixtures of these. Thealkaline earth metal carbonates are a preferred group of particles. Theunit particle is the individual metal carbonate particle and the unitparticle size is the average particle size of the metal carbonateparticles which is readily ascertained, as for example, by conventionalX-ray defraction techniques.

Colloidal disperse systems possessing particles of this type aresometimes referred to as macromolecular colloidal systems.

Because of the composition of the colloidal disperse systems of thisinvention, the metal carbonate particles also exist as components inmicellar colloidal particles. In addition to the metal carbonateparticles and the disperse medium, the colloidal disperse systems of theinvention are characterized by a third essential component, one which issoluble in the medium and contains in the molecules thereof ahydrophobic portion and at least one polar substituent. This thirdcomponent can orient itself along the external surfaces of the abovemetal salts, the polar groups lying along the surface of these saltswith the hydrophobic portions extending from the salts into the dispersemedium forming micellar colloidal particles. These micellar colloids areformed through Weak intermolecular forces, e.g., van der Waals forces,etc. Micellar colloids represent a type of agglomerate particle asdiscussed thereinabove. Because of the molecular orientation in thesemicellar colloidal particles, such particles are characterized by ametal containing layer (i.e., the solid metal-containing particles andany metal present in the polar substituent of the third component, suchas the metal in a sulfonic or carboxylic acid salt group), a hydrophobiclayer formed by the hydrophobic portions of the molecules of the thirdcomponent and a polar layer bridging said metal-containing layer andsaid hydrophobic layer, said polar bridging layer comprising the polarsubstituents of the third component of the system, e.g., the

group if the third component is an alkaline earth metal pe'trosulfonate.

The second essential component of the colloidal disperse system is thedispersing medium. The identity of the medium is not a particularlycritical aspect of the invention as the medium primarily serves as theliquid vehicle in which solid particles are dispersed. The dispersemedium will normally consist of inert organic liquids, that is, liquidswhich are chemically substantially inactive in the particularenvironment in question (the resinous composition). While many of theseinert organic liquids are uonpolar, this is not essential. For example,

many of the plasticizers for the resinous components of the compositionare esters, etc. These polar materials can also be used as thedispersing medium or components thereof. The medium can have componentscharacterized by relatively low boiling points, e.g., in the range of 25to 120 C. to facilitate subsequent removal of a portion or substantiallyall of the medium from the polymeric resin composition or the componentscan have a higher boiling point to protect against removal from theresinous composition upon standing or heating. Obviously, there is nocriticality in an upper boiling point limitation on these liquids.

Representative liquids include the alkanes and haloalkanes of five toeighteen carbons, polyhalo and perhaloalkanes of up to about sixcarbons, the cycloalkanes of five or more carbons, the correspondingalkyland/or halo-substituted cycloalkanes, the aryl hydrocarbons, thealkylaryl hydrocarbons, the haloaryl hydrocarbons, ethers such asdialkyl ethers, alky aryl ethers, cycloalkyl ethers, cycloalkylalkylethers, alkanols, alkylene gylcols, polyalkylene glycols, alkyl ethersof alkylene glycols and polyalkylene glycols, dimethyl formamide,dimethyl acetamide, dibasic alkanoic acid diesters, silicate esters, andmixtures of these. Specific examples include petroleum ether, StoddardSolvent, pentane, hexane, octane, isooctane, undecane, tetradecanecyclopentane cyclohexane, isopropylcyclohexane, 1,4-dimethylcyclohexane,cyclooctane, benzene, toluene, xylene, ethyl benzene tert-butylbenzenehalobenzenes especially monoand polychlorobenzenes such as chlorobenzeneper se and 3,4-di-chlorotoluene, mineral oils, n-propylether,isopropylether, isobutylether, n-amylether, methyl-n-butylether,methyl-namylether cyclohexylether, ethoxycyclohexane, methoxybenzene,isopropoxybenzene, p-methoxytoluene, methanol, ethanol, propanol,isopropanol, hexanol, n-octyl alcohol, n-decl alcohol, alkylene glycolssuch as ethylene glycol and propylene glycol, diethyl ketone, dipropylketone, methylbutyl ketone, acetophenone,1,2-difluoro-tetrachloroethane, dichlorofiuoromethane,1,2-dibromotetrafluoroethane, trichlorofiuoromethane, l-chloropentane,1,3-dichlorohexane, formamide, dimethylformamide, acetamide,dimethylacetamide, diethylacetamide, propionamide, di-isooctyl azelate,ethylene glycol, polypropylene glycols, hexa-2-ethylbutoxy disiloxane,etc.

Also useful as dispersing mediums are the low molecular weight, liquidpolymers, generally classified as oligomers, which include the dimers,tetramers, pentamers, etc. Illustrative of this large class of materialsare such liquids as the propylene tetramers, isobutylene dimers, and thelike.

From the standpoint of availability, cost, and performance, the alkyl,cycloalkyl, and aryl hydrocarbons represent a preferred class ofdisperse mediums. Liquid pe troleum fractions represent anotherpreferred class of disperse mediums. Included within these preferredclasses are benzenes and alkylated benzenes, cycloalkanes and alkylatedcycloalkanes, cyclo-alkenes and alkylated cycloalkenes such as found innaphthene-based petroleum fractions, and the alkanes such as found inthe paraffinbased petroleum fractions. Petroleum ether, naphthas,mineral oils, Stoddard Solvent, toluene, xylene, etc., and mixturesthereof are examples of economical sources of suitable inert organicliquids which can function as the disperse medium in the colloidaldisperse systems of the present invention.

The most preferred disperse systems are those containing at least somemineral oil as a component of the disperse medium. Any amount of mineraloil is beneficial in this respect. However, in this preferred class ofsystems, it is desirable that mineral oil comprise at least about 1% byweight of the total medium, and desirably at least about 5% by weight.Those mediums comprising at least by weight mineral oil are especiallyuseful. As will be seen hereinafter, mineral oil can serve as theexclusive disperse medium. Mineral oils having a viscosity value of fromabout 50 SUS (Saybolt Universal Seconds) at F. to 500 SUS at 210 F. arepreferred. Especially useful are mineral oils of SAE 5 to SAE grade. Thesource of the oils is not critical.

In addition to the solid, metal-containing particles in the dispersemedium, the two essential elements of any disperse system, the dispersesystems employed in the polymeric compositions of the invention requirea third essential component. This third component is an organic compoundwhich is soluble in the disperse medium, and the molecules of which arecharacterized by a hydrophobic portion and at least one polarsubstituent. As explained, infra, the organic compounds suitable as athird component are extremely diverse. These compounds are inherentconstituents of the disperse systems as a result of the methods used inpreparing the systems. Further characteristics of the components areapparent from the following discussion of methods for preparing thecolloidal disperse systems.

Preparation of the disperse systems Broadly speaking, the colloidaldisperse systems of the invention are prepared by treating a singlephase homogeneous, Newtonian system of an overbased, superbased, orhyperbased, organic compound with a conversion agent, usually an activehydrogen containing compound, the treating operation being simply athorough mixing together of the two components, i.e., homogenization.This areatment converts these single phase systems into thenon-Newtonian colloidal disperse systems utilized in conjunction withthe polymeric resins of the present invention.

The terms overbased, superbased, and hyperbased, are terms of art whichare generic to well known classes of metal-containing materials whichhave generally been employed as detergents and/or dispersants inlubricating oil compositions. These overbased materials have also beenreferred to as complexes, metal complexes, high-metal containing salts,and the like. Overbased materials are characterized by a metal contentin excess of that which would be present according to the stoichiometryof the metal and the particular organic compound reacted with the metal,e.g., a carboxylic or sulfonic acid. Thus, if a monosulfonic acid,

R%OH

o is neutralized with a basic metal compound, e.g., calcium hydroxide,the normal metal salt produced will contain one equivalent of calciumfor each equivalent of acid, i.e.,

However, as is well known in the art, various processes are availablewhich result in an inert organic liquid solution of a product containingmore than the stoichiometric amount of metal. The solutions of theseproducts are referred to herein as overbased materials. Following theseprocedures, the sulfonic acid or an alkali or alkaline earth metal saltthereof can be reacted with a metal base and the product will contain anamount of metal in excess of that necessary to neutralize the acid, forexample, 4.5 times as much metal as present in the normal salt of ametal excess of 3.5 equivalents. The actual stoichiometric excess ofmetal can vary considerably, for example, from about 0.1 equivalent toabout 30 or more equivalents depending on the reactions, the processconditions, and the like. These overbased materials useful in preparingthe disperse systems will contain from about 3.5 to about 30 or moreequivalents of metal for each equivalent of material which is overbased.

In the present specification and claims the term overbased is used todesignate materials containing a stoichiometric excess of metal and is,therefore, inclusive of those materials which have been referred to inthe art as overbased, superbased, hyperbased, etc., as discussed supra.

The terminology metal ratio is used in the prior art and herein todesignate the ratio of the total chemical equivalents of the metal inthe overbased material (e.g., a metal sulfonate or carboxylate) to thechemical equivalents of the metal in the product which would be expectedto result in the reaction between the organic material to be overbased(e.g., sulfonic or carboxylic acid) and the metal-containing reactant(e.g., calcium hydroxide, barium oxide, etc.) according to the knownchemical reactivity and stoichiometry of the two reactants. Thus, thenormal calcium sulfonate discussed above, the metal ratio is one and inthe overbased sulfonate, the metal ratio is 4.5. Obviously, if there ispresent in the material to be overbased more than one compound capableof reacting with the metal, the metal ratio of the product will dependupon whether the number of equivalents of metal in the overbased productis compared to the number of equivalents expected to be present for agiven single component or a combination of all such components.

Generally, these overbased materials are prepared by treating a reactionmixture comprising the organic material to be overbased, a reactionmedium consisting essentially of at least one inert, organic solvent forsaid organic material, a stoichiometric excess of a metal base, andpromoter with an acidic material. The methods for preparing theoverbased materials as well as an extremely diverse group of overbasedmaterials are well known in the prior art and are disclosed, for examplein the following U.S. patents: 2,616,904; 2,616,905; 2,616,906;2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,695,910; 2,723,234;2,723,235; 2,723,236; 2,760,970; 2,767,164; 2,767,209; 2,777,874;2,798,852; 2,839,470; 2,856,359; 2,859,360; 2,856,361; 2,861,951;2,883,340; 2,915,517; 2,959,551; 2,968,642; 2,971,014; 2,989,463;3,001,981; 3,027,325; 3,070,581; 3,108,960; 3,147,232; 3,133,019;3,146,201; 3,152,991; 3,155,616; 3,170,880; 3,170,881; 3,172,855;3,194,823; 3,223,630; 3,232,883; 3,242,079; 3,242,080; 3,250,710;3,256,186; sures of these patents disclose exemplary processes forsynthesizing the overbased materials used in producing the dispersesystems of the invention and are, accordingly, incorporated herein byreference for their disclosures of these processes, materials which canbe overbased, suitable metal bases, promoters, and acidic materials, aswell as a variety of specific overbased products.

An important characteristic of the organic materials which are overbasedis their solubility in the particular reaction medium utilized in theoverbasing process. As the reaction medium used previously has normallycomprised petroleum fractions, particularly mineral oils, these organicmaterials have generally been oil-soluble. However, if another reactionmedium is employed (e.g. aromatic hydrocarbons, aliphatic hydrocarbons,kerosene, etc.) it is not essential that the organic material be solublein mineral oil as long as it is soluble in the given reaction medium.Obviously, many organic materials which are soluble in mineral oils willbe soluble in many of the other indicated suitable reaction mediums. Itshould be apparent that the reaction medium usually becomes the dispersemedium of the colloidal disperse system or at least a component thereofdepending on whether or not additional inert organic liquid is added aspart of the reaction medium or the disperse medium.

Materials which can be overbased are generally oilsoluble organic acidsincluding phosphorus acids, thiophosphorus acids, sulfur acids,carboxylic acids, thiocarboxylic acids, and the like, as well as thecorresponding alkali and alkaline earth metal salts thereof.Representative examples of each of these classes of organic acids asWell as other organic acids, e.g., nitrogen acids,

3,274,135. The disclarsenic acids, etc. are disclosed along with methodsof preparing overbased products therefrom in the above cited patent andare, accordingly, incorporated herein by reference. Patent 2,777,874identifies organic acids suitable for preparing overbased materialswhich can be converted to disperse systems for use in the resinouscompositions of the invention. Similarly, 2,616,904; 2,695,910;2,767,164; 2,767,209; 3,147,232; 3,274,135; etc. disclose a variety oforganic acids suitable for preparing overbased materials as well asrepresentative examples of overbased products prepared from such acids.Overbased acids wherein the acid is a phosphorus acid, a thiophosphorusacid, phosphorus acid-sulfur acid combination, and sulfur acid preparedfrom polyolefins are disclosed in 2,883,340; 2,915,517; 3,001,981;3,108,960; and 3,232,883. Overbased phenates are disclosed in 2,959,551while overbased ketones are found in 2,798,852. A variety of overbasedmaterials derived from oil-soluble metalfree, non-tautomeric neutral andbasic organic polar compounds such as esters, amines, amides, alcohols,ethers, sulfides, sulfoxides, and the like are disclosed in 2,968,- 642;2,971,014; and 2,989,463. Another class of materials which can beoverbased are the oil-soluble, nitro-substituted aliphatic hydrocarbons,particularly nitro-substituted polyolefins such as polyethylene,polypropylene, polyisobutylene, etc. Materials of this type areillustrated in 2,959,551. Likewise, the oil-soluble reaction product ofalkylene polyamines such as propylene diamine or N-alkylated propylenediamine with formaldehyde or formaldehyde producing compound (e.g.,paraformaldehyde) can be overbased. Other compounds suitable foroverbasing are disclosed in the above-cited patents or are otherwisewell-known in the art.

The organic liquids used as the disperse medium in the colloidaldisperse system can be used as solvents for the overbasing process.

The metal compounds used in preparing the overbased materials arenormally the basic salts of metals in Group IA and Group IIA of thePeriodic Table although other metals such as lead, zinc, manganese, etc.can be used in the preparation of overbased materials. The anionic portion of the salt can be hydroxyl, oxide, carbonate, hydrogen carbonate,nitrate, sulfite, hydrogen sulfite, halide, amide, sulfate, etc. asdisclosed in the above-cited patents. For purposes of this invention thepreferred overbased materials are prepared from the alkaline earth metaloxides, hydroxidies, and alcoholates such as the alkaline earth metallower alkoxides. The most preferred disperse systems of the inventionare made from overbased materials containing calcium and/or barium asthe metal.

The promoters, that is, the materials which permit the incorporation ofthe excess metal into the overbased material, are also quite diverse andwell known in the art as evidenced by the cited patents. A particularlycomprehensive discussion of suitable promoters is found in 2,777,874;2,695,910; and 2,616,904. These include the alcoholic and phenolicpromoters which are preferred. The alcoholic promoters include thealkanols of one to about twelve carbon atoms such as methanol, ethanol,amyl alcohol, octanol, isopropanol, and mixtures of these and the like.Phenolic promoters include a variety of hydroxy-substituted benzenes andnaphthalenes. A particularly useful class of phenols are the alkylatedphenols of the type listed in 2,777,874, e.g., heptylphenols,octylphenols, and nonylphenols. Mixtures of various promoters aresometimes used.

Carbon dioxide is the acidic material used alone or in combination withother acidic materials to prepare the overbased materials useful inmaking disperse systems suitable as reactants for synthesizing thereaction products of this invention. Ordinarily, carbon dioxide will beused alone. Other known useful acidic materials with which it can beused are liquid acids such as formic acid, acetic acid, nitric acid,sulfuric acid, hydrochloric acid, hydrobromic acid, carbamic acid,substituted carbamic acids,

etc. Acetic acid is a very useful acidic material although inorganicacidic materials such as HCl, S S0 CO H S, N 0 etc., are ordinarilyemployed as the acidic materials.

In preparing overbased materials, the material to be overbased, aninert, non-polar, organic solvent therefor, the metal base, thepromoter, and the acidic material are brought together and a chemicalreaction ensues. The exact nature of the resulting overbased product isnot known. However, it can be adequately described for purposes of thepresent specification as a single phase homogeneous mixture of thesolvent and (1) either a metal complex formed from the metal base, theacidic material, and the material being overbased and/or (2) anamorphous metal salt formed from the reaction of the acidic materialwith the metal base and the material which is said to be overbased.Thus, if mineral oil is used as the reaction medium, petrosulfonic acidas the material which is overbased, Ca(OH) as the metal base, and carbondioxide as the acidic material, the resulting overbased material can bedescribed for purposes of this invention as an oil solution of either ametal containing complex of the acidic material, the metal base, and thepetrosulfonic acid or as an oil solution of amorphous calcium carbonateand calcium petrosulfonate. Since the overbased materials are well-knownand as they are used merely as intermediates in the preperation of thedisperse systems employed herein, the exact nature of the materials isnot critical to the present invention.

The temperature at which the acidic material is contacted with theremainder of the reaction mass depends to a large measure upon thepromoting agent used. With a phenolic promoter, the temperature usuallyranges from about 80 C. to 300 C., and preferably from about 100 C. toabout 200 C. When a alcohol or mercaptan is used as the promoting agent,the temperature usually will not exceed the reflux temperature of thereaction mixture and preferably will not exceed about 100 C.

In view of the foregoing, it should be apparent that the overbasedmaterials may retain all or a portion of the promoter. That is, if thepromoter is not volatile (e.g., an alkyl phenol) or otherwise readilyremovable from the overbased material, at least some promoter remains inthe overbased product. Accordingly, the disperse systems made from suchproducts may also contain the promoter. The presence or absence of thepromoter in the overbased material used to prepare the disperse systemand likewise, the presence or absence of the promoter in the colloidaldisperse systems themselves does not represent a critical aspect of theinvention. Obviously, it is within the skill of the art to select avolatile promoter such as a lower alkanol, e.g., methanol, ethanol,etc., so that the promoter can be readily removed prior to forming thedisperse system or thereafter.

A preferred class of overbased materials used as starting materials inthe preparation of the disperse systems of the present invention are thealkaline earth metaloverbased oil-soluble organic acids, preferablythose containing at least twelve aliphatic carbons although the acidsmay contain as few as eight aliphatic carbon atoms if the acid moleculeincludes an aromatic ring such as phenyl, napthyl, etc. Representativeorganic acids suitable for preparing these overbased materials arediscussed and identified in detail in the above-cited patents.Particularly 2,616,904 and 2,777,874 disclose a variety of very suitableorganic acids. For reasons of economy and performance, overbasedoil-soluble carboxylic and sulfonic acids are particularly suitable.Illustrative of the carboxylic acids are palmitic acid, stearic acid,myristic acid, oleic acid, linoleic acid, behenic acid,hexatriacontanoic acid, tetrapropylene-substituted glutaric acid,polyisobutene (M.W.-5000)-substituted succinic acid, polypropylene(M.W.5000)-substituted succinic acid, polytadecyl-substituted adipicacid, chlorostearic acid, 9- methyl-stearic acid, dichlorostearic acid,stearylbenzoic acid, eicosane-substituted naphthoic acid,dilauryl-decahydronaphthalene carboxylic acid, didodecyl-tetralincarboxylic acid, dioctyl-cyclohexane carboxylic acid, mixtures of theseacids, their alkali and alkaline earth metal salts, and/ or theiranhydrides. Of the oil-soluble sulfonic acids, the mono-, di-, andtri-aliphatic hydrocarbon substituted aryl sulfonic acids and thepetroleum sulfonic acids (petrosulfonic acids) are particularlypreferred. Illustrative examples of suitable sulfonic acids includemahogany sulfonic acids, petrolatum sulfonic acids,monoeicosane-substituted naphthalene sulfonic acids, dodecylbenzenesulfonic acids, didodecylbenzene sulfonic acids, dinonylbenzene sulfonicacids, cetyl-chlorobenzene sulfonic acids, dilauryl beta-naphthalenesulfonic acids, the sulfonic acid derived by the treatment ofpolyisobutene having a molecular weight of 1500 with chlorosulfonicacid, nitronaphthalenesulfonic acid, paraffin wax sulfonic acid,cetyl-cyclopentane sulfonic acid, laurylcyclo-hexanesulfonic acids,polyethylene (M.W.750) sulfonic acids, etc. Obviously, it is necessarythat the size and number of aliphatic groups on the aryl sulfonic acidsbe sufficient to render the acids soluble. Normally the aliphatic groupswill be alkyl and/or alkenyl groups such that the total number ofaliphatic carbons is at least twelve.

Within this preferred group of overbased carboxylic and sulfonic acids,the barium and calcium overbased mono-, di-, and tri-alkylated benzeneand naphthalene (including hydrogenated forms thereof), petrosulfonicacids, and higher fatty acids are especially preferred. Illustrative ofthe synthetically produced alkylated benzene and naphthalene sulfonicacids are those containing alkyl substituents having from 8 to about 30carbon atoms therein. Such acids include di-isododecyl-benzene sulfonicacid, wax-substituted phenol sulfonic acid, wax-substituted benzenesulfonic acids, polybutene-substituted sulfonic acid,cetyl-chloro-benzene sulfonic acid, di-cetylnaphthalene sulfonic acid,di-lauryldiphenylether sulfonic acid, diisonouylbenzene sulfonic acid,di-isooctadecylbenzenesul' fonic acid, stearylnaphthalene sulfonic acid,and the like. The petroleum sulfonic acids are a well known artrecognized class of materials which have been used as starting materialsin preparing overbased products since the inception of overbasingtechniques as illustrated by the above patents. Petroleum sulfonic acidsare obtained by treating refined or semi-refined petroleum oils withconcentrated or fuming sulfuric acid. These acids remain in the oilafter the settling out of sludges. These petroleum sulfonic acids,depending on the nature of the petroleum oils from which they areprepared, are oil-soluble alkene sulfonic acids, and alkyl, alkaryl, oraralkyl subfonic acids including cycloalkyl sulfonic acids andcycloalkene sulfonic acids, and alkyl, lakaryl, or aralkyl substitutedhydrocarbon aromatic sulfonic acids including single and condensedaromatic nuclei as well as partially hydrogenated forms thereof.Examples of such petrosulfonic acids include mahogany sulfonic acid,white oil sulfonic acid, petrolatum sulfonic acid, petroleum naphthenesulfonic acid, etc. This especially preferred group of aliphatic fattyacids includes the saturated and unsaturated higher fatty acidscontaining from 12 to about 30 carbon atoms. Illustrative of these acidsare lauric acid, palmitic acid, oleic acid, linoleic acid, linolenicacid, oleo-stearic acid, stearic acid, myristic acid, and undecalinicacid, alphachlorostearic acid, and alphanitrolauric acid.

As shown by the representative examples of the preferred classes ofsulfonic and carboxylic acids, the acids may contain non-hydrocarbonsubstituents such as halo, nitro, alkoxy, hydroxyl, and the like.

It is desirable that the overbased materials used to prepare thedisperse system have a metal ratio of at least about 3.5 and preferablyabout 4.5. An especially suitable group of the preferred sulfonic acidoverbased materials has a metal ratio of at least about 7.0. Whileoverbased materials having a metal ratio of 75 have been prepared,normally the maximum metal ratio will not exceed about 30 and, in mostcases, not more than about 20.

The overbased materials used in preparing the colloidal disperse systemsutilized in the polymeric compositions of the invention contain fromabout to about 70% by weight of metal-containing components. Asexplained hereafter, the exact nature of these metal containingcomponents is not known. It is theorized that the metal base, the acidicmaterial, and the organic material being overbased form a metal complex,this complex being the metal-containing component of the overbasedmaterial. On the other hand, it has also been postulated that the metalbase and the acidic material form amorphous metal compounds which aredissolved in the inert organic reaction medium and the material which issaid to be overbased. The material which is overbased may itself be ametal-containing compound, e.g., a carboxylic or sulfonic acid metalsalt. In such a case, the metal-containing components of the overbasedmaterial would be both the amorphous compounds and the acid salt. Theexact nature of these overbased materials is obviously not critical inthe present invention since these materials are used only asintermediates. The remainder of the overbased materials consistessentially of the inert organic reaction medium and any promoter whichis not removed from the overbased product. For purposes of thisapplication, the organic material whch is subjected to overbasing isconsidered a part of the metal containing components. Normally, theliquid reaction medium constitutes at least about 30% by weight of thereaction mixture utilized to prepare the overbased materials.

As mentioned above, the colloidal disperse systems used in thecomposition of the present invention are prepared by homogenizing aconversion agent and the overbased starting material. Homogenization isachieved by vigorous agitation of the two components, preferably at thereflux temperature or a temperature slightly below the refluxtemperature. The reflux temperature normally will depend upon theboiling point of the conversion agent. However, homogenization may beachieved within the range of about 25 C. to about 200 C. or slightlyhigher. Usually, there is no real advantage in exceeding 150 C.

The concentration of the conversion agent necessary to achieveconversion of the overbased material is usually within the range of fromabout 1% to about 80% based upon the weight of the overbased materialexcluding the weight of the inert, organic solvent and any promoterpresent therein. Preferably at least about 10% and usually less thanabout 60% by weight of the conversion agent is employed. Concentrationsbeyond 60% appear to afford no additional advantages.

The terminology conversion agent as used in the specification and claimsis intended to describe a class of very diverse materials which possessthe property of being able to convert the Newtonian homogeneous,singlephase, overbased materials into non-Newtonian colloidal dispersesystems. The mechanism by which conversion is accomplished is notcompletely understood. However, with the exception of oxygen, carbondioxide, air and mixtures of two or more of these, these conversionagents all possess active hydrogens. The conversion agents include loweraliphatic carboxylic acids, water, aliphatic alcohols, cycloaliphaticalcohols, arylaliphatic alcohols, phenols, ketones, aldehydes, amines,boron acids, phosphorus acids, oxygen, air, and carbon dioxide. Mixturesof two or more of these conversion agents are also useful. Particularlyuseful conversion agents are discussed below.

The lower aliphatic carboxylic acids are those containing less thanabout eight carbon atoms in the molecule. Examples of this class ofacids are formic acid, acetic acid, propionic acid, butyric acid,valeric acid, isovaleric acid, isobutyric acid, caprylic acid, heptanoicacid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, etc.Formic acid, acetic acid, and propionic acid, are preferred with aceticacid being especially suitable. It is to be understood that theanhydrides of these acids are also useful and, for the purposes of thespecification and claims of this invention, the term acid is intended toincludeboth the acid per se and the anhydride of the acid.

Useful alcohols include aliphatic, cycloaliphatic, and arylaliphaticmonoand polyhydroxy alcohols. Alcohols having less than about twelvecarbons are especially useful while the lower alkanols, i.e., alkanolshaving less than about eight carbon atoms are preferred for reasons ofeconomy and effectiveness in the process. Illustrative are the alkanolssuch as methanol, ethanol, isopropanol, n-propanol, isobutanol, tertiarybutanol, isooctanol, dodecanol, n-pentanol, etc; cycloalkyl alcoholsexemplified by cyclopentanol, cyclohexanol, 4-methylcyclohexanol, 2-cycohexylethanol, cyclopentylmethanol, etc.; phenyl aliphatic alkanolssuch as benzyl alcohol, 2-phenylethanol, and cinnamyl alcohol; alkyleneglycols of up to about six carbon atoms and mono-lower alkyl ethersthereof such as monomethylether of ethylene glycol, diethylene glycol,ethylene glycol, trimethylene glycol, hexamethylene glycol, triethyleneglycol, 1,4-butanedio, 1,4-cyclohexanediol, glycerol, andpentaerythritol.

The use of a mixture of water and one or more of the alcohols isespecially effective for converting the overbased materials to colloidaldisperse systems. Such combinations often reduce the length of timerequired for the process. Any water-alcohol combination is effective buta very etfective combination is a mixture of one or more alcohols andwater in a weight ratio of alcohol to water of from about 0.05:1 toabout 24:1. Preferably, at least one lower alkanol is present in thealcohol component of these water-alkanol mixtures. Water-alkanolmixtures wherein the alcoholic portion is one or more lower alkanols areespecially suitable. Alcoholzwater conversions are illustrated inapplicants copending application Ser. No. 535,693, filed Mar. 21, 1966,now US. 3,372,115.

Phenols suitable for use as conversion agents include phenol, naphthol,ortho-cresol, para-cresol, catechol, mixtures of cresol,para-tert-butylphenol, and other lower alkyl substituted phenols,meta-polyisobutene(M.W.- 35 0)-substituted phenol, and the like.

Other useful conversion agents include lower aliphatic aldehydes andketones, particularly lower alkyl aldehydes and lower alkyl ketones such:as acetaldehydes, propionaldehydes, butyraldehydes, acetone,methylethyl ketone, diethyl ketone. Various aliphatic, cycloaliphatic,aromatic, and heterocyclic amines are also useful providing they containat least one amino group having at least one active hydrogen attachedthereto. Illustrative of these amines are the monodi-alkylamines,particularly monoand di-lower alkylamines, such as methylamine,ethylamine, propylamine, dodecylamine, methyl ethylamine, diethylamine;the cycloalkylamines such as cyclohexylamine, cyclopentylamine, and thelower alkyl substituted cycloalkylamines such as3-methylcyclohexylamine; 1,4- cyclohexylenediamine; arylamines such asaniline, mono-, di-, and tri-, lower alkyl-substituted phenyl amines,naphthylamines, 1,4-phenylene diamines; lower alkanol amines such asethanolamine and diethanolamine; alkylenediamines such as ethylenediamine, triethylene tetramine, propylene diamines, octamethylenediamines; and heterocyclic amines such as piperazine,4-aminoethylpiperazine, 2-octadecyl-imidazoline, and oxazolidine. Boronacids are also useful conversion agents and include boronic acids (e.g.,alkyl-B(OH) or aryl-B(OH boric acid (i.e., H BO tetraboricacid,metaboric acid, and esters of such boron acids.

The phosphorus acids are useful conversion agents and include thevarious alkyl and aryl phosphinic acids, phosphinus acids, phosphonicacids, and phosphonous acids. Phosphorus acids obtained by the reactionof lower alkanols or unsaturated hydrocarbons such as polyisobuteneswith phosphorus oxides and phosphorus sulfides are particularly useful,e.g., P 0 and P 8 Oxygen, carbon dioxide, air, and various mixtures ofoxygen and carbon dioxide can be used as conversion agents. However, itis preferable to use these conversion agents in combination with one ormore of the foregoing 13 conversion agents. For example, the combinationof water and carbon dioxide is particularly effective as a conversionagent for transforming the overbased materials into a colloidal dispersesystem.

As previously mentioned, the overbased materials are single phasehomogeneous systems. However, depending on the reaction conditions andthe choice of reactants in preparing the overbased materials, theresometimes is present in the product insoluble contaminants. Thesecontaminants are normally unrea-cted basic materials such as calciumoxide, barium oxide, calcium hydroxide, barium hydroxide, or other metalbase materials used as a reactant in preparing the overbased material.It has been found that a more uniform colloidal disperse system resultsif such contaminants are removed prior to homogenizing the overbasedmaterial with the conversion agents. Obviously a more uniform dispersesystem makes it possible to achieve reproducibility of properties inresinous compositions containing such systems. Accordingly, it ispreferred that any insoluble contaminants in the overbased materials beremoved prior to converting the material in the colloidal dispersesystem. The removal of such contaminants is easily accomplished byconventional techniques such as filtration or centrifugation. It shouldbe understood however, that the removal of these contaminants, whiledesirable for reasons just mentioned, is not an absolute essentialaspect of the invention and useful products can be obtained whenoverbased materials containing insoluble contaminants are converted tothe colloidal disperse systems.

The conversion agents or a proportion thereof may be retained in thecolloidal disperse system. The conversion agents are however, notessential components of these disperse systems and it is usuallydesirable that as little of the conversion agents as possible beretained in the disperse systems. Since these conversion agents do notreact with the overbased material in such a manner as to be permanentlybound thereto through some type of chemical bonding, it is normally asimple matter to remove a major proportion of the conversion agents and,generally, substantially all of the conversion agents. Some of theconversion agents have physical properties which make them readilyremovable from the disperse systems. Thus, most of the free carbondioxide and/or oxygen gradually escape from the disperse system duringthe homogenization process or upon standing thereafter. Since the liquidconversion agents are generally more volatile than the remainingcomponents of the disperse system, they are readily removable byconventional devolatilization techniques, e.g., heating, heating atreduced pressures, and the like. For this reason, it may be desirable toselect conversion agents which will have boiling points which are lowerthan the remaining components of the disperse system. This is anotherreason why the lower alkanols, mixtures thereof, and lower alkanol-watermixtures are preferred conversion agents.

Again, it is not essential that all of the conversion agent be removedfrom the disperse systems. In fact, useful disperse systems foremployment in the resinous compositions of the invention result withoutremoval of the conversion agents. However, from the standpoint ofachieving uniform results, it is generally desirable to remove theconversion agents, particularly where they are volatile. In some cases,the liquid conversion agents may facilitate the mixing of the colloidaldisperse system with the polymeric resin material. In such cases, it isadvantageous to permit the conversion agents to remain in the dispersesystem until it is mixed with the polymeric resin. Thereafter, theconversion agents can be removed from the mixture of the disperse systemand polymeric resins by conventional devolatilization techniques ifdesired.

To better illustrate the colloidal disperse systems utilized in theinvention, the procedure for preparing a preferred system is describedbelow:

The overbased material As stated above, the essential materials forpreparing an overbased product are (1) the organic material to beoverbased, (2) an inert, non-polar organic solvent for the organicmaterial, (3) a metal base, (4) a promoter, and (5) an acidic material.In this example, these materials are 1) calcium petrosulfonate, (2)mineral oil, (3) calcium hydroxide, (4) a mixture of methanol,isobutanol, and n-pentanol, and (5) carbon dioxide.

A reaction mixture of 1305 grams of calcium sulfonate having a metalratio of 2.5 dissolved in mineral oil, 220 grams of methyl alcohol, 72grams of isobutanol, and 38 grams of n-pentanol is heated to 35 C. andsubjected to the following operating cycle four times: mixing with 143grams of calcium hydroxide and treating the mixture with carbon dioxideuntil it has a base number of 3239. The resulting product is then heatedto 155 C. during a period of 9 hours to remove the alcohols and thenfiltered at this temperature. The filtrate is a calcium overbasedpetrosulfonate having a metal ratio of 12.2.

Conversion to a colloidal disperse system A mixture of 150 parts of theoverbased material, 15 parts of methyl alcohol, 10.5 parts of n-pentanoland 45 parts of water is heated under reflux conditions at 71 74 C. for13 hours. The mixture becomes a gel. It is then heated to 144 over aperiod of 6 hours and diluted with 126 parts of mineral oil having aviscosity of 2000 SUS at F. and the resulting mixture heated at 144 C.for an additional 4.5 hours with stirring. This thickened product is acolloidal disperse system of the type contemplated by the presentinvention.

The .disperse systems of the invention are characterized by threeessential components: (A) solid, metal-containing particles formed insitu, (B) an inert, non-polar, organic liquid which functions as thedisperse medium, and (C) an organic compound which is soluble in thedisperse medium and the molecules of which are characterized by ahydrophobic portion and at least one polar substituent. In the colloidaldisperse system described immediately above, these components are asfollows: (A) calcium carbonate in the form of solid particles, (B)mineral oil, and (C) calcium petrosulfonate.

From the foregoing example, it is apparent that the solvent for thematerial which is overbased becomes the colloidal disperse medium or acomponent thereof. of course, mixtures of other inert liquids can besubstituted for the mineral oil or used in conjunction with the mineraloil prior to forming the overbased material. Moreover, after theoverbased material is prepared, additional liquid material can be addedif desired, to form a part of the disperse medium.

It is also readily seen that the solid, metal-containing particlesformed in situ possess the same chemical composition as would thereaction products of the metal base and the acidic material used inpreparing the overbased materials. Thus, the actual chemical identity ofthe metal containing particles formed in situ depends upon both theparticular metal base or bases employed and the particular acidicmaterial or materials reacted therewith. For example, if the metal baseused in preparing the overbased material is barium oxide and if theacidic material is carbon dioxide, the metal-containing particles formedin situ would comprise barium carbonate.

However, the physical characteristics of the particles formed in situ inthe conversion step are quite different from the physicalcharacteristics of any particles present 1n the homogeneous,single-phase overbased material whlch is subjected to the conversion.Particularly, such physical characteristics as particle size andstructure are quite different. The solid, metal-containing particles ofthe colloidal disperse systems are of a size sufficient for detection byX-ray diffraction. The overbased materials 15 prior to conversion arenot characterized by the presence of these detectable particles.

X-ray diifraction and electron microscope studies have been made of bothoverbased organic materials and colloidal disperse systems preparedtherefrom. These studies establish the presence in the disperse systemsof the soild, metal-containing salts. For example, in the dispersesystem prepared herein above, the calcium carbonate is present as solidcalcium carbonate having a particle size of about 40 to 50 A. (unitparticle size) and interplanar spacing (dA.) of 3.035. But X-raydiffraction studies of the overbased material from which it was preparedindicate the absence of calcium carbonate of this type. In fact, calciumcarbonate present as such, if any, appears to be amorphous and insolution. While applicant does not intend to be bound by any theoryoffered to explain the changes which accompany the conversion step, itappears that conversion permits particle formation and growth. That is,the amorphous, metal-containing apparently dissolved salts or complexespresent in the overbased material form solid, metal-containing particleswhich by a process of particle growth become colloidal particles. Thus,in the above example, the dissolved amorphous calcium carbonate salt orcomplex is transformed into solid particles which then grow. In thisexample, they grow to a size of 40 to 50 A. In many cases, theseparticles apparently are crystallites. Regardless of the correctness ofthe postulated mechanism for in situ particle formation the fact remainsthat no particles of the type predominant in the disperse systems arefound in the overbased materials from which they are prepared.Accordingly, they are unquestionably formed in situ during conversion.

As these solid metal-containing particles formed in situ come intoexistance, they do so as pre-wet, predispersed solid particles which areinherently uniformly distributed throughout the other components of thedisperse system. The liquid disperse medium containing these pre-wetdispersed particles is readily mixed with the acidic esters of thephosphoric acids to prepare the products of this invention. Thispre-wet, pre-dispersed character of the solid metal-containing particlesresulting from their in situ formation is, thus, an extremely importantfeature of the disperse systems.

In the foregoing example, the third component of the disperse system(i.e., the organic compound which is soluble in the disperse medium andwhich is characterized by molecules having a hydrophobic portion and apolar substituent) is calcium petrosulfonate,

wherein R is the residue of the petrosulfonic acid. In this case, thehydrophobic portion of the molecule is the hydrocarbon moiety ofpetrosulfonic, i.e., R The polar substituent is the metal salt moity,

The hydrophobic portion of the organic compound is a hydrocarbon radicalor a substantially hydrocarbon radical containing at least about twelvealiphatic carbon atoms. Usually the hydrocarbon portion is an aliphaticor cycloaliphatic hydrocarbon radical although aliphatic orcycloaliphatic substituted aromatic hydrocarbon radicals are alsosuitable. In other words, the hydrophobic portion of the organiccompound is the residue of the organic material which is overbased minusits polar substituents. For example, if the material to be overbased isa carboxylic acid, sulfonic acid, or phosphorus acid, the hydrophobicportion is the residue of these acids which would result from theremoval of the acid functions. Similarly, if the material to beoverbased is a phenol, a nitro-substituted polyolefin, or an amine, thehydrophobic portion of the organic compound is the radical resultingfrom the removal of the hydroxyl, nitro, or amino group respectively. Itis the hydrophobic portion of the molecule which renders the organiccompound soluble in the solvent used in the overbasing process and laterin the disperse medium.

Obviously, the polar portion of these organic compounds are the polarsubstituents such as the acid salt moiety discussed above. When thematerial to be overbased contains polar substituents which will reactwith the basic metal compound used in overbasing, for example, acidgroups such as carboxy, sulfino, hydroxysulfonyl, and phosphorus acidgroups or hydroxyl groups, the polar substituent of the third componentis the polar group formed from the reaction. Thus, the polar substituentis the corresponding acid metal salt group or hydroxyl group metalderivative, e.g., an alkali or alkaline earth metal sul-fonate,carboxylate, sulfinate, alcoholate, or phenate.

On the other hand, some of the materials to be overbased contained polarsubstituents which ordinarily do not react with metal bases. Thesesubstituents include nitro, amino, ketocarboxyl, carboalkoxy, etc. Inthe disperse systems derived from overbased materials of this type thepolar substituents in the third component are unchanged from theiridentity in the material which was originally overbased.

The identity of the third essential component of the disperse systemdepends upon the identity of the starting materials (i.e., the materialto be overbased and the metal base compound) used in preparing theoverbased material. Once the identity of these starting materials isknown, the identity of the third component in the colloidal dispersesystem is automatically established. Thus, from the identity of theoriginal material, the identity of the hydrophobic portion of the thirdcomponent in the disperse system is readily established as being theresidue of that material minus the polar substituents attached thereto.The identity of the polar substituents on the third component isestablished as a matter of chemistry. If the polar groups on thematerial to be overbased undergo reaction with the metal base, forexample, if they are acid functions, hydroxy groups, etc., the polarsubstituent in the final product will correspond to the reaction productof the original substituent and the metal base. On the other hand, ifthe polar substituent in the material to be overbased is one which doesnot react with metal bases, then the polar substituent of the thirdcomponent is the same as the original substituent.

As previously mentioned, this third component can orient itself aroundthe metal-containing particles to form micellar colloidal particles.Accordingly, it can exist in the disperse system as an individual liquidcomponent dissolved in the disperse medium or it can be associated withthe metal-containing particles as a component of micellar colloidalparticles.

The acidic esters of phosphoric acids are a well-known class of organiccompounds which are derived from phosphorus containing reactants such asphosphorus pentoxide, phosphorus oxychloride, phosphoric acids,polyphosphoric acids, etc., and an alcoholic or phenolic compound of thetype ROH according to known procedures. The term acidic ester isintended to encompass those esters wherein there is at least one acidhydrogen atom attached through an oxygen (i.e., H-O) to phosphorus inthe ester molecules. Accordingly, the acidic esters are monoor diestersof phosphoric acids.

The alcoholic and phenolic compounds which can be used to prepare theacidic esters are selected from the monoand polyhydric aliphaticalcohols including cycloaliphatic alcohols, aliphatic substitutedphenols, and mixtures of these including mixtures of aliphatic alcohols,mixtures of cycloaliphatic alcohols, mixtures of aliphaticsubstitutedphenols, and mixtures of any of these.

17 Accordingly, in the compound ROH, R is an aliphatic, cycloaliphatic,aryl or aliphatic substituted aryl radical. Preferably, these arehydrocarbon or hydroxy-substituted hydrocarbon radicals. In other words,the alcoholic portion of the acidic esters, i.e., OR, is the oxy radicalwhich is the residue of the alcohol after removal of the hydroxylhydrogen. Normally the alcoholic portion will be hydrocarbyloxy orhydroxy-substituted hydrocarbyloxy. The alcohols and phenols representedby the formula ROH normally contain up to about forty carbons although,in the case of polymeric alcohols and phenols or polymer substitutedalcohols and phenols, molecular weights of up to about 10,000 areacceptable. Suitable members of the group ROH include the monoandpolyhydric alkanols and alkenols containing up to about ten hydroxygroups, preferably those having up to thirty carbons; monoand polyhydriccycloaliphatic alcohols, particularly those containing and 6 carbons inthe rings thereof including cycloalkanols, cycloalkenols,cycloalkylsubstituted alkanols and alkenols, cycloalkenyl-substitutedalkanols and alkenols, aliphatic hydrocarbon substituted (e.g., alkyl,alkenyl, or olefin polymer substituted) cyclo aliphatic alcohols of thetype indicated immediately above; phenols, naphthols, and aliphatichydrocarbon-substituted phenols and naphthols wherein the aliphaticsubstituent can be alkyl, alkenyl, or olefin polymer substituent, etc.In addition to the hydroxy groups present in these alcohols and phenols,other substituents such as ether linkages (--O), lower alkoxy, loweralkenoxy, alkyl mercapto, alkenyl mercapto, halo, carbo hydrocarbyloxy(e.g.,

hydrocarbyl), nitro, etc., may be present so long as they do notinterfere with the formation of the acidic phos phorus esters.

Representative phenolic compounds of the formula ROH are phenol,2-chlorophenol beta-naphthols, alphanaphthols, cresol, resorcinol,catechol, P,P'-dihydroxy biphenyl, and the corresponding aliphatichydrocarbon-substituted phenolic compounds such as 2,4-dibutylphenol,propenetetramer substituted phenol, didodecylphenol, diisooctyl phenol,hexylresorcinol, alkyl-substituted 4,4- methylene-bis-phenol,alpha-decyl-beta-uaphthol, polyisobutene (molecular weight-1000)substituted phenol, polypropylene (molecular weightl500) substitutedphenol, 4- cyclohexylphenol. Aliphatic hydrocarbon substituted phenolscharacterized by a molecular weight of up to about 100,000 andpreferably up to about 5000 having from one to three aliphatichydrocarbon substituents constitute a preferred class of phenoliccompounds.

The aliphatic hydrocarbon substituent may be an alkyl substituent suchas methyl, ethyl, isopropyl, n-butyl, tertbutyl, n-amyl, isoamyl,tert-amyl, n-hexyl, decyl, dodecyl. Other low molecular weightsubstituents include the unsaturated radicals such as allyl, propargyl,etc.

The sources of the s'ubstitutent also include the substantiallysaturated polymers of mono-olefins having from 2 to about 8 carbonatoms. The especially useful polymers are the polymers of l-mono-olefinssuch as ethylene, propene, l-butene, isobutene, and l-hexane. Polymersof medial olefins, i.e., olefins in which the olefinic linkage is not atthe terminal position, likewise are useful. They are illustrated byZ-butene, 3-pentene, and 4-oc.t,ene.

Also useful as substituents are the interpolymers of the olefins such asthose illustrated above with other interpolymerizable olefinicsubstances such as cyclic olefins, and polyolefins. Such interpolymersinclude, for example, those prepared by polymerizing isobutene withbutadiene; propene with isoprene; ethylene with piperylene; isobutenewith chloroprene; l-hexene with 1,3- hexadiene; l-octene with l-hexene;l-heptene with 'l-pentene; 3'-methyl-1-butene with l-octene;3,3-dimethyl-1- pentene with l-hexene; etc.

The relative proportions of the mono-olefins to the other monomers inthe interpolymers influence the stability and oil-solubility of thefinal acidic, phosphorus-containing compositions derived from suchinterpolymers. Thus, for reasons of oil-solubility and stability theinterpolymers should be aliphatic and substantially saturated, i.e.,they should contain about perferably at least about 95%, on a Weightbasis of units derived from the aliphatic mono-olefins and no more thanabout 5% of olefinic linkages based on the total number ofcarbon-tocarbon covalent linkages. In most instances, the percentage ofolefinic linkages should be less than about 24% of the total number ofcarbon-to-carbon covalent linkages.

Specific examples of such interpolymers include copolymers of 95% (byWeight) of isobutene with 5% of l-hexene; terpolymer of 98% of isobutenewith 1% of piperylene and 1% of chloroprene; terpolymer of 95% ofisobutene with 2% of l-butene and 3% of l-hexene; terpolymer of 60% ofisobutene with 20% of l-pentene and 20% of l-octene; copolymer of 80% ofl-hexene and 20% of l-heptene; terpolymer of of isobutene with 2% ofcyclohexene and 8% of propene; and copolymer of 80% of ethylene and 20%of propene.

The aliphatic hydrocarbon-substituted phenols may be the monoor thepoly-substituted phenols, i.e., phenols having two or more substituents.A convenient method for preparing the high molecular weight substitutedphenols comprises the alkylation of phenol with the olefin polymer inthe presence of a Friedel-Crafts catalyst such as boron fluoride,aluminum chloride, aluminum bromide, ferric chloride, zinc chloride,diatomaceous earth, or the like. In lieu of the olefin polymer, ahalogenated olefin polymer may be used to alkylate the phenol. In thelatter method the olefin polymer is first, e.g., chlorinated to aproduct having one or more atomic proportions of chlorine per moleculeof the olefin polymer and the chlorinated olefin polymer is then allowedto react with the phenol in the presence of a Friedel-Crafts catalyst.More than one mole of the olefin polymer may be made to react withphenol so that the product may contain two or three olefin polymersubstituents. The preparation of the substituted phenols by these andother methods is wellknown in the art and need not be described here ingreater detail.

Other suitable alcohols of the formula ROH include methanol, ethanol,isooctanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol,hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol,betaphenylethyl alcohol, Z-methylcyclohexanol, beth-chloroethanol,monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol,monopropyl ether of diethylene glycol, monododecyl ether of triethyleneglycol, monooleate of ethylene glycol, monostearate of diethyleneglycol, secpentyl alcohol, tert-butyl alcohol, 5-bromododecanol,nitro-octadecanol and dioleate of glycerol. The polyhydric alcoholspreferably contain from 2 to about 10 hydroxy radicals. They areillustrated by, for example, ethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, dipropylene glycol,tripropylene glycol, dibutylene glycol, tributylene glycol, and otheralkylene glycols in which the alkylene radical contains from 2 to about8 carbon atoms. Other useful polyhydric alcohols include glycerol,mono-oleate of glycerol, monostearate of glycerol, monomethyl ether ofglycerol, pentaerythritol, 9,10-dihydroxy stearic acid, methyl ester of9,10-dihydroxy stearic acid, 1,2-butanediol, 2,3-hexanediol,2,4-hexanediol, pinacol, erythritol, arbitol, sorbitol, mannitol,1,2-cyclohexanediol, and xylylene glycol. Carbohydrates such as sugars,starches, celluloses, etc., likewise may yield the esters of thisinvention. The carbohydrates may be exemplified by a glucose, fructose,sucrose, rhamose, mannose, glyceraldehyde, and galactose.

The esters of this invention may also be derived from unsaturatedalcohols such as allyl alcohol, cinnamyl alcohol, proparagyl alcohol,l-cyclohexen-S-ol, an oleyl alcohol. Still other classes of the alcoholscapable of yielding the esters of this invention comprises theetheralcohols and amino-alcohols including, for example, theoxy-alkylene-, oxy-arylene-, amino-alkylene-, andaminoarylene-substituted alcohols having one or more oxyalkylene,amino-alkylene or amino-arylene oxy-arylene radicals. They areexemplified by Cellosolve, Carbitol, phenoxyethanol,heptylphenyl-(oxypropylene) H, octyl- (oxyethylene -H, phenyloxyoctylene-H, mono (heptylphenyl-oxypropylene)-substituted glycerol, poly(styreneoxide), amino-ethanol, 3-amino ethylpentanol, di(hydroxyethyl)amine,p-aminophenol, tri(hydroxypropyl) amine, N-hydroxyethyl ethylenediamine, N,N,N,N-tetrahydroxytrimethylene diamine, and the like. Of thisgroup, the etheralcohols having up to about 15 oxy-alkylene radicals inwhich the alkylene radical contains from 1 to about 8 carbon atoms areprefe red.

Various processes for producing acidic esters of phosphoric acids arewell known in the art. Suitable acidic esters and/or processes for theirpreparation are disclosed in patents 2,005,619; 2,341,565; 2,360,302;2,698,835; 3,050,487 and 3,055,865. Acidic esters can be preparedaccording to the process disclosed in 3,254,111 by elminating theneutralization step employed therein.

It should be understood that the acidic acid esters used as reactants inthe present invention can be a given monoor diester or a mixture ofdifferent mono-and/ or diesters or a mixture comprising triesters aswell as these acidic esters. However, it is preferred to maintain theester reactant free from the triesters insofar as possible as they willnot function as reactants. Obviously, the weight of the triesters isexcluded in determining the weight of acidic acid ester reactant to beemployed.

Thus, the acidic phosphorus-containing esters useful in the preparationof the compositions of this invention can be prepared by the reaction ofa phenolic composition with phosphorus pentoxide. Phosphoric acid (i.e.,dehydrated phosphorus pentoxide) may be used in lieu of the pentoxide.The molar ratio of the phenolic composition to the phosphorus pentoxidein the reaction should be within the range of from about 1:1 to :1, thepreferred ratio being from 2:1 to 4: 1. The reaction is efifected simplyby mixing the two reactants at a temperature between about 50 C. and 90C. In some instances, the temperature may be 150 C. to 200 C. or higher,but ordinarily it is below 100 C. Unreacted phenolic compound can beremoved or allowed to remain in the acidic ester product which isreacted with the disperse system. The reaction is preferably carried outin the presence of a solvent which facilitates temperature control andmixing of the reactants. The solvent may be any inert fluent substancein which either one or both reactants are soluble, or the product issoluble. Examples of such solvents include aryl hydrocarbons such asbenzene, toluene, or xylene; aliphatic hydrocarbons such as n-hexane,cyclohexane, or naphtha; or polar solvents such as diethyl ether,carbitol, dibutyl ether, dioxane, chlorobenzene, nitrobenzene, carbontetrachloride or chloroform.

The product of the above reaction is acidic and is a mixture of acidicphosphates consisting predominantly of the monoand the di-esters ofphosphoric acids, the ester radical (i.e. alcoholic portion, OR) beingderived from the hydroxy compound, ROI-I.

Another preferred class of acidic phosphorus-containing esters can beobtained by the reaction of phosphorus pentoxide or a phosphoric acidwith a mixture of an aliphatic hydrocarbon substituted phenol and acopolymer of allyl alcohol and a styrene. The reaction mechanism bywhich the acidic ester product is formed is not completely understoodbut probably involves a reaction between the phosphorus pentoxide andthe copolymer of allyl alcohol and a styrene, followed then by reactionof this intermediate product with the substituted phenol. The optimumreaction time is about 4 to 6 hours although a suitable product can beobtained at any point within a period of from about 1 to 10 hours.

The copolymer of allyl alcohol and a styrene preferably is a lowmolecular weight copolymer prepared from an approximately equimolarmixture of the two monomers. The molecular weight of the copolymershould be within the range of from about 500 to about 5000. A particularpreference is expressed for a copolymer of approximately equimolaramounts of allyl alcohol and styrene having a molecular weight of about1100 to 1500.

The term a styrene as used herein refers to styrene or any of thevarious substituted styrenes such as halogensubstituted styrenes,hydrocarbon-substituted styrenes, alkoxy-styrenes, acyloxy-styrenes,nitro-styrenes, etc. Examples of such substituted styrenes includepara-chlorostyrene, para-ethyl styrene, o-phenylstyrene,p-methoxystyrene, m-nitrostyrene, alpha-methyl-styrene, and the like. Inmost instances, however, it is preferred to use styrene itself by reasonof its low cost, commercial availability, and excellence as a rawmaterial in the preparation of the acidic phosphorus-containingcompositions.

The reaction of phosphorus pentoxide with a hydrocarbon substitutedphenol and the copolymer of allyl alcohol and a styrene is carried outsimply by mixing the specified reactants, preferably with a solvent, andheating the resulting solution at a temperature within the range of fromabout 75 C. to 150 C. until the reaction is complete. The earlieststages of the overall reaction produce a cloudy, thickened reactionmixture but as reaction proceeds further, this is changed to arelatively clear, nonviscous solution. The solvent may be removed ifdesired, but generally the above solution is incorporated into thecompositions of this invention with the solvent.

The following examples illustrate various overbased materials, coloidaldisperse systems prepared from these overbased materials and preparationof the compounds of this invention. Unless otherwise indicated,percentages and parts refer to percent by weight and parts by weight.Where temperatures exceed the boiling points of the components of thereaction mixture, obviously reflux conditions are employed unless thereaction products are being heated to remove'volatile components.Examples 1 through 43 are directed to the preparation of over basedmaterials illustrative of the types which can be used to prepare thenon-Newtonian colloidal disperse systems used in the polymeric resinouscompositions of the invention. The term naphtha as used in the followingexamples refers to petroleum distillates boiling in the range of aboutC. to about C. and usually designated Varnish Makers and PaintersNaphtha,

EXAMPLE 1 To a mixture of 3,245 grams (12.5 equivalents) of a mineraloil solution of barium petroleum sulfonate (sulfate ash of 7.6%), 32.5parts of octylphenol, 197 parts of water, there is added 73 parts ofbarium oxide within a period of 30 minutes at 5784 C. The mixture isheated at 100 C. for 1 hour to remove substantially all water and blownwith 75 parts of carbon dioxide at 133 to C. within a period of 3 hours.A mixture of 1,000 grams of the above carbonated intermediate product,121.8 parts of octylphenol, and 234 parts of barium hydroxide is heatedat 100 C. and then at 150 C. for 1 hour. The mixture is then blown withcarbon dioxide at 150 C. for 1 hour at a rate of 3 cubic feet per hour.The carbonated product is filtered and the filtrate is found to have asulfate ash content of 39.8% and a metal ratio of 9.3.

EXAMPLE 2 To a mixture of 3,245 grams (12.5 equivalents) of bariumpetroleum sulfonate, 1,460 grams (7.5 equivalents) of heptylphenol, and2,100 grams of water in 8,045 grams of mineral oil there is added at C.7,400 grams (96.5 equivalents) of barium oxide. The addition of bariumoxide causes the temperature to rise to 143 C. which temperature ismaintained until all the water has been distilled. The mixture is thenblown with carbon dioxide 21 until it is substantially neutral. Theproduct is diluted with 5,695 grams of mineral oil and filtered. Thefiltrate is found to have a barius sulfate ash content of 30.5% and ametal ratio of 8.1. Another inert liquid such as benzene, toluene,heptene, etc., can be substituted for all or part of the mineral oil.

EXAMPLE 3 EXAMPLE 4 A stirred mixture of 57 grams (0.4 equivalents) ofnonyl alcohol and 3.01 grams (3.9 equivalents) of barium oxide is heatedat 150175 C. for an hour, then cooled to 80 C. whereupon 400 grams (12.5equivalents) of methanol is added. The resultant mixture is stirred at70- 75 C. for 30 minutes, then treated with 1,285 grams (1.0 equivalent)of 40% barium petroleum sulfonate. This mixture is stirred at refluxtemperature for an hour, then treated with carbon dioxide at 60-70 C.for 2 hours. The mixture is then heated to 160 C. at a pressure of 18millimeters of mercury and thereafter filtered. The filtrate is a clear,brown oily material having the following analysis: sulfate ash, 32.5%;neutralization numbernil; metal ratio, 4.7.

EXAMPLE 5 (a) To a mixture of 1,145 grams of a mineral oil solution of a40% solution of barium mahogany sulfonates (1.0 equivalent) and 100grams of methyl alcohol at 55 C., there is added 220 grams of bariumoxide while the mixture is being blown with carbon dioxide at a rate of2 to 3 cubic feet per hour. To this mixture there is added an additional78 grams of methyl alcohol and then 460 grams of barium oxide while themixture is blown with carbon dioxide. The carbonated product is heatedto 150 C. for 1 hour and filtered. The filtrate is found to have abarium sulfate ash content of 53.8% and a metal ratio of 8.9.

(b) A carbonated basic metal salt is prepared in accordance with theprocedure of (a) except that a total of 16 equivalents of barium oxideis used per equivalent of the barium mahogany sulfonate. The productpossesses a metal ratio of 13.4.

EXAMPLE 6 A mixture of 520 parts (by weight) of a mineral oil, 480 partsof a sodium petroleum sulfonate (molecular weight of 480), and 84 partsof water is heated at 100 C. for 4 hours. The mixture is then heatedwith 86 parts of a 76% aqueous solution of calcium chloride and 72 partsof lime (90% purity) at 100 C. for 2 hours, dehydrated by heating to awater content of less than 0.5%, cooled to 50 C., mixed with 130 partsof methyl alcohol, and then blown with carbon dioxide at 50 C. untilsubstantially neutral. The mixture is then heated to 150 C. to removethe methyl alcohol and water and the resulting oil solution of the basiccalcium sulfonate filtered. The filtrate is found to have a calciumsulfate ash content of 16% and a metal ratio of 2.5.

A mixture of 1,305 grams of the above carbonated calcium sulfonate, 930grams of mineral oil, 220 grams of methyl alcohol, 72 grams of isobutylalcohol, and 38 grams of primary amyl alcohol is prepared, heated to 35C., and subjected to the following operating cycle 4 times: mixing with143 grams of 90% calcium hydroxide and treating the mixture with carbondioxide until it has a base number of 32-39. The resulting product isthen heated to 155 C. during a period of 9 hours to remove the alcoholsand filtered through a siliceous filter aid at this temperature. Thefiltrate has a calcium sulfate ash content of 39.5% and a metal ratio of12.2.

EXAMPLE 7 A basic metal salt is prepared by the procedure described inExample 6 except that the slightly basic calcium sulfonate having ametal ratio of 2.5 is replaced with a mixture of that calcium sulfonate(280 parts by weight) and tall oil acid (970 parts by weight having anequivalent weight of 340) and that the total amount of calcium hydroxideused is 930 parts by weight. The resulting highly basic metal salt ofthe process has a calcium sulfate ash content of 48%, a metal ratio of7.7, and an oil content of 31%.

EXAMPLE 8 A highly basic metal salt is prepared by the procedure ofExample 7 except that the slightly basic calcium sulfonate startingmaterial having a metal ratio of 2.5 is replaced with tall oil acids(1,250 parts by weight, having an equivalent weight of 340) and thetotal amount of calcium hydroxide used is 772 parts by weight. Theresulting highly basic metal salt has a metal ratio of 5.2, a calciumsulfate ash content of 41%, and an oil content of 33%.

EXAMPLE 9 A normal calcium mahogany sulfonate is prepared by metathesisof a 60% oil solution of sodium mahogany sulfonate (750 parts by weight)with a solution of 67 parts of calcium chloride and 63 parts of water.The reaction mass is heated for 4 hours at to C. to effect theconversion of the sodium mahogany sulfonate to calcium mahoganysulfonate. Then 54 parts of lime is added and the whole is heated to C.over a period of 5 hours. When the whole has cooled to 40 C., 98 partsof methanol is added and 152 parts of carbon dioxide is introduced overa period of 20 hours at 4243 C. Water and alcohol are then removed byheating the mass to 150 C. The residue in the reaction vessel is dilutedwith 100 parts of low viscosity mineral oil. The filtered oil solutionof the desired carbonated calcium sulfonate overbased material shows thefollowing analysis: sulfate ash content, 16.4%; neutralization number,0.6 (acidic); and a metal ratio of 2.50. By adding barium or calciumoxide or hydroxide to this product with subsequent carbonation, themetal ratio can be increased to a ratio of 3.5 or greater as desired.

EXAMPLE 10 A mixture of 880 grams (0.968 moles) of a 57.5% oil solutionof the calcium sulfonate of tridecylbenzene bottoms (the bottomsconstitute a mixture of mono-, di-, and tri-decylbenzene), 149 grams ofmethanol, and 59 grams (1.58 equivalents) of calcium hydroxide areintroduced into a reaction vessel and stirred vigorously. The whole isheated to 4045 C. and carbon dioxide is introduced for 0.5 hour at therate of 2 cubic feet per hour. The carbonated reaction mixture is thenheated to 150 C. to remove alcohol and any water present, and theresidue is filtered for purposes of purification. The product, a 61% oilsolution of the desired overbased carbonated calcium sulfonate materialshows the following analysis: ash content, 16.8%; neutralization number,7.0 (acidic); and metal ratio, 2.42. By further carbonation in thepresence of an alkali or alkaline earth metal oxide, hydroxide, oralkoxide, the metal ratio can readily be increased to 3.5 or greater.

EXAMPLE 1 l A mixture of 2,090 grams (2.0 equivalents) of a 45% oilsolution of calcium mahogany sulfonate containing 1% of water, 74 grams(2.0 equivalents) of calcium hydroxide, and 251 grams of ethylene glycolis heated for 1 hour at 100 C. Carbon dioxide is then bubbled throughthe mixture at 40-45 C. for 5.5 hours. The ethylene glycol and any waterpresent are removed by heating the mixture to a tempearture of 185 C. at10.2 millimeters of mercury. The residue is filtered yielding thedesired overbased calcium sulfonate material, having the follow inganalysis: sulfate ash, 12.9%; neutralization number 5.0 (acidic); and ametal ratio of 2.0 which can be increased to 3.5 or greater as desiredby carbonation in the presence of calcium oxide or hydroxide.

EXAMPLE 12 A mixture comprising 1,595 parts of the overbased material ofExample 9 (1.54 equivalents based on sulfonic acid anion), 167 parts ofthe calcium phenate prepared as indicated below (0.19 equivalent), 616parts of mineral oil, 157 parts of 91% calcium hydroxide (3.86equivalents), 288 parts of methanol, 88 parts of isobutanol, and 56parts of mixed isomeric primary-amyl alcohols (containing about 65%normal amyl, 3% isoamyl and 32% of Z-methyl-l-butyl alcohols) is stirredvigorously at 40 C. and 25 parts of carbon dioxide is introduced over aperiod of 2 hours at 40-50 C. Thereafter, three additional portions ofcalcium hydroxide, each amounting to 1.57 parts, are added and each suchaddition is followed by the introduction of carbon dioxide as previouslyillustrated. After the fourth calcium hydroxide addition and thecarbonation step is completed, the reaction mass is carbonated for anadditional hour at 43-47 C. to reduce neutralization number of the massto 4.0 (basic). The substantially neutral, carbonated reaction mixtureis freed from alcohol and any water of reaction by heating to 150 C. andsimultaneously blowing it with nitrogen. The residue in the reactionvessel is filtered. The filtrate, an oil solution of the desiredsubstantially neutral, carbonated calcium sulfonate overbased materialof high metal ratio, shows the following analysis: sulfate ash content,41.11%; neutralization number 0.9 (basic); and a metal ratio of 12.55.

The calcium phenate used above is prepared by adding 2,250 parts ofmineral oil, 960 parts (5 moles) of heptylphenol, and 50 parts of waterinto a reaction vessel and stirring at 25 C. The mixture is heated to 40C. and 7 parts of calcium hydroxide and 231 parts (7 moles) of 91%commercial parafomaldehyde is added over a period of 1 hour. The wholeis heated to 80 C. and 200 additional parts of calcium hydroxide (makinga total of 207 parts or 5 moles) is added over a period of 1 hour at80-90 C. The whole is heated to 150 C. and maintained at thattemperature for 12 hours while nitrogen is blown through the mixture toassist in the removal of water. If foaming is encountered, a few dropsof polymerized dimethyl silicone foam inhibitor may be added to controlthe foaming. The reaction mass is then filtered. The filtrate, a 33.6%oil solution of the desired calcium phenate of heptylphenol-formaldehydecondensation product is found to contain 7.56% sulfate ash.

EXAMPLE 13 A mixture of 574 grams (0.5 equivalent) of 40% bariumpetroleum sulfonate, 98 grams (1.0 equivalent) of furfuryl alcohol, and762 grams of mineral oil is heated with stirring at 100 C. for an hour,then treated portionwise over a 15-minute period with 230 grams (3.0equivalents) of barium oxide. During this latter period, the temperaturerises to 120 C. (because of the exothermic nature of the reaction ofbarium oxide and the alcohol). The mixture then is heated to ISO-160 C.for an hour, and treated subsequently at this temperature for 1.5 hourswith carbon dioxide. The material is concentrated by heating to atemperature of 150 C. at a pressure of millimeters of mercury andthereafter filtered to yield a clear, oil-soluble filtrate having thefollowing analyses: sulfate ash content, 21.4%; neutralization number,2.6 (basic); and a metal ratio of 6.1.

EXAMPLE 14 An overbased material is prepared by the procedure of Example6 except that the slightly basic calcium sulfonate starting material hasa metal ratio of 1.6 and the amount of this calcium sulfonate used is1050 parts (by Weight) and the total amount of lime used is 630 parts.The resulting metal salt has a calcium sulfate ash content of 40%, aratio of the inorganic metal group to the bivalent bridging group of 16,and an oil content of 35%.

EXAMPLE 15 To a mixture of 1614 parts (3 equivalents) of apolyisobutenyl succinic anhydride (prepared by the reaction of achlorinated polyisobutene having an average chlorine content of 4.3% andan average of 67 carbon atoms with maleic anhydride at about 200 C.),4313 parts of mineral oil, 345 parts (1.8 equivalents) of heptylphenol,and 200 parts of water, at 0., there is added 1,038 parts (24.7equivalents) of lithium hydroxide monohydrate over a period of 0.75 hourwhile heating to C. Isooctanol (75 parts) is added while the mixture isheated to C. over a 1.5 hour period. The mixture is maintained at ISO-C. and blown with carbon dioxide at the rate of 4 cubic feet per hourfor 3.5 hours. The reaction mixture is filtered through a filter aid andthe filtrate is the desired product having a sulfate ash content of18.9% and a metal ratio of 8.0.

EXAMPLE 16 The procedure of Example 6 is repeated except that anequivalent amount of sodium hydroxide is used in lieu of the calciumoxide. The product is the corresponding sodium overbased material.

EXAMPLE 17 A mixture of 244 parts (0.87 equivalent) of oleic acid, partsof primary isooctanol, and 400 parts of mineral oil is heated to 70 C.whereupon 172.6 parts (2.7 equivalents) of cadmium oxide is added. Themixture is heated for 3 hours at a tempearture of 150 to 160 C. whileremoving water. Barium hydroxide monohydrate (324 parts, 3.39equivalents) is then added to the mixture over a period of 1 hour whilecontinuing to remove water by means of a side-arm water trap. Carbondioxide is blown through the mixture at a temperature of from 150-160 C.until the mixture is slightly acidic to phenolphthalein. Upon completionof the carbonation, the mixture is stripped to a temperature of 150 C.at 35 mm. of mercury to remove substantially all the remaining water andalcohol. The residue is the desired overbased product containing bothbarium and cadmium metal.

EXAMPLE 18 The procedure of Example 13 is repeated except that thebarium sulfonate is replaced by an equivalent amount of potassiumsulfonate, and potassium oxide is used in lieu of the barium oxideresulting in the preparation of the corresponding potassium overbasedmaterial.

EXAMPLE 19 A sulfoxide is prepared by treating polyisobutylene (averagemolecular weight 750) with 47.5% of its weight of SOC1 for 4.5 hours at220 C. A mixture of 787 grams (1.0 equivalent) of this sulfoxide, 124grams (0.6 equivalent) of diisobutylphenol, 550 grams of mineral oil,and 200 grams of water was warmed to 70 C. and treated with 360 grams(4.0 equivalents) of barium oxide. This mixture is heated at refluxtemperature for 1 hour and treated at 150 C. with carbon dioxide untilthe mixture is substantially neutral and thereafter filtered to yield aclear, oil-soluble liquid having the following analyses: sulfate ash,22.8%; neutralization number, 5.8 (basic); and metal ratio, 5.8.

EXAMPLE 20 To a mixture of 268 grams (1.0 equivalent) of oleyl alcohol,675 grams of mineral oil, 124 grams (0.6 equivalent) ofdiisobutylphenol, and 146 grams of water, at 70 C. there is added 308grams (4.0 equivalents) of barium oxide. This mixture is heated atreflux temperature for 1 hour, then at 150 C. while bubbling carbondioxide therethrough until substantial neutrality of the mixture isachieved. The resulting reaction mass is filtered resulting in a clear,brown oil-soluble filtrate having the following analysis: sulfate ashcontent, 29.8%; neutralization number 2.6 (basic); and metal ratio, 6.0.

EXAMPLE 21 To a mixture of 423 grams (1.0 equivalent) of sperm oil, 124grams (0.6 equivalent) of heptylphenol, 500 grams of mineral oil, and150 grams of water there are added at 70 C. 308 grams (4.0 equivalents)of barium oxide. This mixture is heated at reflux temperature for 1hour, dried by heating at about 150 C. and thereafter carbonated bytreatment with carbon dioxide at the same temperature until the reactionmass was slightly acidic. Filtration yields a clear, light brown,nonviscous overbased liquid material having the following analysis:sulfate ash content, 32.0%; neutralization number 0.5 (basic) metalratio, 6.5.

EXAMPLE 22 To a mixture of 174 grams (1.0 equivalent) of N-octadecylpropylene diamine, 124 grams (0.6 equivalent) of diisobutylphenol, 766grams of mineral oil, 146 grams of water, there are added 306 grams (4.0equivalents) of barium oxide and the whole is refluxed for an hour.Water is subsequently removed by raising the temperature to 150 C. andthereafter carbon dioxide is bubbled therethrough while maintaining thistemperature. When the reaction mass is substantially neutral, carbondioxide addition is ceased and the reaction mass filtered producing aclear, oil-soluble liquid having the following analysis: sulfate ashcontent, 28.9%; neutralization number, 2.5 (basic); metal ratio, 5.8.

EXAMPLE 23 A mixture of 6000 grams of a 30% solution of barium petroleumsulfonate (sulfate ash 7.6%), 348 grams of para-tertiary butylphenol,and 2911 grams of water are heated to a temperature of 60 C. whileslowly adding 1100 grams of barium oxide and raising the temperature to94-98 C. The temperature is held within this range for about 1 hour andthen slowly raised over a period of 7 /2 hours to 150 C. and held atthis level for an additional hour assuring substantial removal of allwater. The resulting overbased material is a brown liquid having thefollowing analysis: Sulfate ash content, 26.0%; metal ratio, 4.35.

This product is then treated with S until 327 grams of the mass combinedwith the overbased material. The product thus obtained has aneutralization number of zero. The SO -treated material was liquid andbrown in color.

One thousand grams of the SO -treated overbased material producedaccording to the preceeding paragraph is mixed with 286 grams of waterand heated to a temperature of about 60 C. Subsequently, 107.5 grams ofbarium oxide are added slowly and the temperature is maintained at 9498C. for 1 hour. Then the total reaction mass is heated to 150 C. over a1% hour period and held there for a period of 1 hour. The resultingoverbased material is purified by filtration, the filtrate being thebrown, liquid overbased material having the following analysis: sulfateash content, 33.7%; basic number, 38.6%; metal ratio, 6.3.

26 EXAMPLE 24 (a) A polyisobutylene having a molecular weight of 700-800is prepared by the aluminum chloride-catalyzed polymerization ofisobutylene at 030 C., is nitrated with a 10% excess (1.1 moles) of 70%aqueous nitric acid at 7075 C. for 4 hours. The volatile components ofthe product mixture are removed by heating at 75 C. at a pressure of 75mm. of mercury. To a mixture of 151 grams (0.19 equivalent) of thisnitrated polyisobutylene, 113 grams (0.6 equivalents) of heptylphenol,155 grams of water, and 2,057 grams of mineral oil there is added at 70C. 612 grams (8 equivalents) of barium oxide. This mixture is heated at150 C. for an hour, then treated with carbon dioxide at this sametemperature until the mixture is neutral (phenolphthalein indicator;ASTM D-974-53T procedure at 25 C.; a measurement of the degree ofconversion of the metal reactant, i.e., barium oxide, bicarbonation).The product mixture is filtered and the filtrate found to have thefollowing analysis: sulfate ash content, 27.6%; percent N, 0.06; andmetal ratio, 9.

(b) A mixture of 611 grams (0.75 mole) of the nitrated polyisobutyleneof Example 1, 96 grams (0.045 mole) of heptylphenol, 2104 grams ofmineral oil, 188 grams of water and 736 grams (4.8 moles) of bariumoxide was heated at reflux temperature for an hour. The water wasvaporized and carbon dioxide passed into the mixture at 150 C. until themixture was no longer basic. This carbonated mixture was filtered andthe clear fluid filtrate showed the following analysis: Sulfate ashcontent, 26.3%; percent N, 0.15; base No. 2.4; metal ratio, 6.7.

EXAMPLE 25 (a) A mixture of 1 equivalent of a nitrated polypropylenehaving a molecular weight of about 3000, 2 equivalents of cetylphenol,mineral oil, and 3 equivalents of barium hydroxide is heated at refluxtemperature for 1 hour. The temperature is then raised to 150 C. andcarbon dioxide is bubbled through the mixture at this temperature. Thereaction product is filtered and the filtrate is the desired overbasedmaterial.

(b) A solvent-refined, acid-treated Pennsylvania petroleum lubricatingoil is nitrated by treatment with 1.5 moles of 70% aqueous nitric acidat 5478 C. for 8 hours. After removal of volatile components of theproduct mixture by heating at 103 C. at a pressure of 15 mm. of mercuryfor 2 hours, a 787 gram portion (1.0 equivalent) of the nitrated productis treated with 2 grams (0.3 equivalent) of heptylphenol, 495 grams ofmineral oil, grams of water, and 378 grams (5 equivalents) of bariumoxide. This mixture is heated at reflux temperature for an hour, thenfreed of water by distillation. The temperature is increased to 150 C.whereupon carbon dioxide is bubbled into the mixture until it isneutral. Filtration yields a clear filtrate with the following analysis:percent sulfate ash, 27.6; percent N, 0.5; and metal ratio, 3.1.

EXAMPLE 26 (a) A mixture of 1000 parts of mineral oil, 2 equivalents afbarium hydroxide, 1 equivalent of 1-nitro-3-octadecyl-cyclohexane and 1equivalent (i.e., 0.5 mole) of 4,4'-methylene-bis (heptylphenol) iscarbonated at C. for 4 hours until the reaction mixture is substantiallyneutral to phenolphthalein indicator. The reaction mass is filtered andthe desired product is the filtrate.

(b) A mixture of 1000 parts of mineral oil, 3 equivalents of lithiumhydroxide, 1 equivalent of nitrated polyisobutene (prepared by mixing500 parts by weight of polyisobutene having an average molecular Weightof 1000 and 62.5 parts of 67% aqueous nitric acid at 6570 C. for 11hours) and para-butylphenol (1 equivalent) is carbonated according tothe technique of (a) above to produce the corresponding lithiumoverbased material.

27 EXAMPLE 27 A copolymer of isobutene and piperylene (weight ratio of98.2) having a molecular weight of about 2000, is nitrated by theprocedure used in the preceding example for the nitration ofpolyisobutene. An overbased product is then prepared from this nitratedreactant by mixing 1 equivalent thereof with 1 equivalent ofa-butyl-fi-naphthyl and 7 equivalents barium hydroxide, diluting themixture with mineral oil to a 50% oil mixture, and then carbonating themixture at 120-160 C. until it is substantially neutral tophenolphthalein indicator. The reaction product is filtered and thefiltrate is the desired overbased product.

EXAMPLE 28 A mixture of 630 grams (2 equivalents) of a rosin amine(consisting essentially of dehydroabietyl amine) having a nitrogencontent of 44% and 245 grams (1.2 equivalents) of heptylphenol having ahydroxyl content of 8.3% is heated to 90 C. and thereafter mixed with230 grams (3 equivalents) of barium oxide at 90140 C. The mixture ispurged with nitrogen at 140 C. A 600 gram portion is diluted with 400grams of mineral oil and filtered. The filtrate is blown with carbondioxide, diluted with benzene, heated to remove the benzene, mixed withxylene, and filtered. The filtrate, a xylene solution of the product hasa barium sulfate ash content of 25.1%, a nitrogen content of 2%, and areflux base number of 119. (The basicity of the metal composition isexpressed in terms of milligrams of KOH which are equivalent to one gramof the composition.) For convenience, the basicity thus determined isreferred to in the specification as a refiux base number.

EXAMPLE 29 An amine-aldehyde condensation product is obtained asfollows: formaldehyde (420 grams, 14 moles) is added in small incrementsto a mixture comprising N-octadecylpropyledediamine (1392 grams, 4moles), mineral oil (300 grams), water (200 grams), and calciumhydroxide (42 grams-condensation catalyst) at the reflux temperature,i.e., 100-105 C. The rate of addition of formaldehyde is such as toavoid excessive foaming. The mixture is heated at reflux temperature for1 hour, slowly heated to 155 C., and blown with nitrogen at 150-155 C.for 2 hours to remove all volatile components. It is then filtered. Thefiltrate, 93% of the theoretical yield, is a 65.4% oil solution of theamine-aldehyde condensation product having a nitrogen content of 2.4%.

A 1,850 gram portion (3.2 equivalents of nitrogen) is mixed with 1,850grams of heptylphenol (0.97 equivalent), 1,485 grams of mineral oil, and1,060 grams of 90% pure barium oxide (12.6 equivalents) and heated to 70C. Over a period of 1 hour, 500 grams of water is added whilemaintaining the temperature in the range of 70 100 C. The mixture isheated at 110 to 115 C. for 4.7 hours and thereafter to 150 C. Whilemaintaining the temperature within the range of 140150 C., the reactionmixture is carbonated and subsequently filtered. The filtrate is a 57.8%oil solution of the overbased amine-aldehyde condensation product havinga nitrogen content of 0.87% and a barium sulfate ash content of 29.5%.

EXAMPLE A partially acylated polyamine reactant is prepared as follows:a mixture (565 parts by weight) of an alkylene amine mixture consistingof triethylene tetramine and diethylene triamine in weight ratio of 3:1is added at 20- 80 C. to a mixture of naphthenic acid having an acidnumber of 180 (1,270 parts) and oleic acid (1,110 parts). The totalquantity of the two acids used is such as to provide 1 equivalent ofacid for each two equivalents of the amine mixture used. The reaction isexothermic. The mixture is blown with nitrogen while it is being heatedto 240 C. in 4.5 hours and thereafter heated at 28 this temperature for2 hours. Water is collected as the distillate.

To the above residue, ethylene oxide (140 parts) is added at 170180 C.within a period of 2 hours while nitrogen is bubbled through thereaction mixture. Nitrogen blowing is continued for an additional 15minutes and the reaction mixture then diluted with 940 parts of xyleneto a solution containing 25% by weight of xylene. The resulting solutionhas a nitrogen content of 5.4% and a base number of 82 at pH of 4, thelatter being indicative of free amino groups.

A 789 gram portion of the above xylene solution (3 equivalents ofnitrogen) is heated to 150 C. at a pressure of 2 millimeters of mercuryto distill off xylene and is then mixed with 367 grams of heptylphenol(having a hydroxyl content of 8.3%; 1.8 equivalents). To this mixturethere is added 345 grams (4.5 equivalents) of barium oxide in smallincrements at -111 C. The mixture is heated at 90-120 C. for 2.5 hoursand blown with carbon dioxide for 1.75 hours. It is diluted with gramsof xylene and then heated at C. for 3.5 hours. It is then diluted with20% by weight of xylene and filrtered. The filtrate has a barium sulfateash content of 33.2%, a nitrogen content of 3.52% and a reflux basenumber of 134.

EXAMPLE 31 To a mixture of 408 grams (2 equivalents) of heptylphenolhaving a hydroxy content of 8.3% and 264 grams of xylene there is added3 83 grams (5 equivalents) of barium oxide in small increments at 85-110C. Thereafter, 6 grams of water is added and the mixture is carbonatedat 100-130 C. and filtered. The filtrate is heated to 100 C. dilutedwith xylene to a 25% xylene solution. This solution has a barium sulfateash content of 41% and a reflux base number of 137.

EXAMPLE 32 A mixture of 5846 parts (4.0 equivalents) of a neutralcalcium sulfonate having a calcium sulfate ash content of 4.68% (66%mineral oil), 464 parts =(2.4 equivalents) of heptylphenol, and 3.4parts of water is heated to 80 C. whereupon 1,480 parts (19.2equivalents) of barium oxide is added over a period of 0.6 hour. Thereaction is exothermic and the temperature of the reaction mixturereaches 100 C. The mixture is heated to 150 C. and carbonated at thistemperature. During the carbonation, 24 parts of barium chloride wereadded to the mixture. Oil was removed from the reaction mixture duringthe carbonation procedure. carbonation is continued at this temperatureuntil the mixture has a base number (phenolphthalein) of 80. Octylalcohol (164 parts) and a filter aid are added to the mixture and themixture is filtered while hot. The filtrate is the desired overbasedbarium bright stock sulfonate having a barium sulfate ash content of26.42, a metal ratio of 4.6 and a refiux base number of 104.

EXAMPLE 33 Following the procedure for preparing barium and calciumoverbased sulfonates exemplified above, sodium mahogany sulfonate (0.26equivalent), 1 equivalent of phenol, and 5.3 equivalents of strontiumoxide are carbonated until the reaction mixture is almost neutral. Theresulting overbased material is filtered, the filtrate being the desiredproduct and having a metal ratio of 4.6.

EXAMPLE 34 A barium overbased carboxylic acid is prepared by carbonatinga mixture of 9.8 equivalents of barium hydroxide, 1 equivalent ofheptylphenol, and 0.81 equivalent of a polyisobutene substitutedsuccinic anhydride wherein the polyisobutenyl portion thereof has anaverage molecular weight of 1000.

29 EXAMPILE 3s A mixture of 1000 parts by weight of a polyisobutenehaving a molecular weight of 1000 and 90 parts of phosphorouspentasulfide is prepared at room temperature, heated to 260 C. overhours, and maintained .at this temperature for an additional 5 hours.The reaction mass is then cooled to 106 C. and hydrolyzed by treatmentwith steam at this temperature for 5 hours. The hydrolyzed acid has aphosphorous content of 2.4%, a sulfur content of 2. 8%. In a separatevessel, a mixture of oil and barium hydroxide is prepared by mixing 2200parts of a mineral oil and 1150 parts of barium oxide at 88 C. andblowing the mixture with steam for 3 hours at 150 C. To this mixturethere is added portionwise throughout a period of 3 hours, 1,060 partsof the above hydrolyzed acid while maintaining the temperature at145-150 C., and then 360 parts of heptylphenol is added over a 1.5 hourperiod. The resulting mixture is blown with carbon dioxide at the rateof 100 parts per hour for 3 hours at 150-15-7 C. The carbonated productis mixed with 850 parts of a mineral oil and dried by blowing it withnitrogen at a temperature of 150 C. The dry product is filtered and thefiltrate is diluted with mineral oil to a solution having a bariumsulfate ash content of 25%. The final solution has a phosphorous contentof 0.38%, a sulfur content of 0.48%, a neutraliza tion number less than5 (basic), a reflux base number of 109, and a metal ratio of 7.2.

EXAMPLE 3 6 To a mixture of 268 grams (1.0 equivalent) of oleyl alcohol,124 grams (0.6 equivalent) of heptylphenol, 988 grams of mineral oil,and 160 grams of water there is added 168 grams (4.0 equivalents) oflithium hydroxide monohydrate. The mixture is heated at refluxtemperature for an hour and then carbonated at 150 C. until it issubstantially neutral. The filtration of this carbonated mixture yieldsa liquid having a lithium sulfate content of 12.7%.

(B) To a mixture of 1614 parts (3 equivalents) of a polyisobutenylsuccinic anhydride prepared by the reaction of a chlorinatedpolyisobutene having an average chlorine content of 4.3% and an averageof 67 carbon atoms with maleic anhydride at about 200 0., 4,313 parts ofmineral oil, 345 parts (1.8 equivalents) of heptylphenol, and 200 partsof water, at 80 0, there is added 1,038 parts (24.7 equivalents) oflithium hydroxide monohydrate over a period of 0.75 hour while heatingto 105 C. Isooctanol (75 parts) is added while the mixture is heated to150 C. in about 1.5 hours. The mixture is maintained at 150-170 C. andblown with carbon dioxide at the rate of 4 cubic feet per hour for 3.5hours. The reaction mixture is filtered through a filter aid and thefiltrate is the desired product having a sulfate ash content of 18.9 anda metal ratio of 8.

EXAMPLE 37 A thiophosphorus acid is prepared as set forth in Example 35above. A mixture of 890 grams of this acid (0.89 equivalent), 2,945grams of mineral oil, 445 grams of heptylphenol (2.32 equivalents), and874 grams of lithium hydroxide monohydrate (20.8 equivalents) formed byadding the metal base to the mineral oil solution of the acid and theheptylphenol over a 1.5 hour period maintaining the temperature at100-110 C. and thereafter drying at 150 C. for 2 hours, carbon dioxideis bubbled therethrough at the rate of 4 cubic feet per hour until thereaction mixture was slightly acidic to phenolphthalein, about 3.5hours, while maintaining the temperature within the range of 150-160 C.The reaction mixture is then filtered twice through a diatomaceous earthfilter. The filtrate is the desired lithium overbased thio-phosphorousacid material having a metal ratio of 6.3.

30 EXAMPLE 3:;

(a) A reaction mixture comprising 2,442 grams (2.8 equivalents) ofstrontium petrosulfonate, 3,117 grams of mineral oil, grams ofisooctanol, and 910 grams of methanol is heated to 55 C. and thereafter615 grams of strontium oxide (11.95 equivalents) is added over a 10minute period while maintaining the reaction at a temperature of 55 -65C. The mixture is heated an additional hour at this same temperaturerange and thereafter blown with carbon dioxide at a rate of 4 cubic feetper hour for about 3 hours until the reaction mixture was slightlyacidic to phenolphthalein. Thereafter the reaction mixture is heated toC. and held there for about 1 hour while blowing the nitrogen at 5 cubicfeet per hour. Thereafter, the product is filtered, the filtrate beingthe desired overbased material having a metal ratio of 3.8.

(b) To a mixture of 3800 parts (4 equivalents) of a 50% mineral oilsolution of lithium petroleum sulfonate (sulfate ash of 6.27%), 460parts (2.4 equivalents) of heptylphenol, 1,920 parts of mineral oil, and300 parts of water, there is added at 70 C. 1,216 parts (28.9equivalents) of lithium hydroxide monohydrate over a period of 0.25hour. This mixture is stirred at 110 C. for 1 hour, heated to 150 C.over a 2.5 hour period, and blown with carbon dioxide at the rate of 4cubic feet per hour over a period of about 3.5 hours until the reactionmixture is substantially neutral. The mixture is filtered and thefiltrate is the desired product having a sulfate ash content of 25.23%and a metal ratio of 7.2.

EXAMPLE 39 A mixture of alkylated benzene sulfonic acids and naphtha isprepared by adding 1000 grams of a mineral oil solution of the acidcontaining 18% by weight mineral oil (1.44 equivalents of acid) and 222grams of naphtha. While stirring the mixture, 3 grams of calciumchloride dissolved in 90 grams of water and 53 grams of Mississippi lime(calcium hydroxide) is added. This mixture is heated to 97-99 C. andheld at this temperature for 0.5 hour. Then 80 grams of Mississippi limeare added to the reaction mixture with stirring and nitrogen gas isbubbled therethrough to remove water. While heating to 150 C. over a 3hour period. The reaction mixture is then cooled to 50 C. and grams ofmethanol are added. The resulting mixture is blown with carbon dioxideat the rate of 2 cubic feet per hour until substantially neutral. Thecarbon dioxide blowing is discontinued and the water and methanolstripped from the reaction mixture by heating and bubbling nitrogen gastherethrough. While heating to remove the water and methanol, thetemperature rose to 146 C. over a 1.75 hour period. At this point themetal ratio of the overbased material was 2.5 and the product is aclear, dark brown viscous liquid. This material is permitted to cool to50 C. and thereafter 1256 grams thereof is mixed with 574 grams ofnaphtha, 222 grams of methanol, 496 grams of Mississippi lime, and 111grams of an equal molar mixture of isobutanol and amyl alcohol. Themixture is thoroughly stirred and carbon dioxide is blown therethroughat the rate of 2 cubic feet per hour for 0.5 hour. An additional 124grams of Mississippi lime is added to the mixture with stirring and theCO blowing continued. Two additional 124 gram increments of Mississippilime are added to the reaction mixture while continuing the carbonation.Upon the addition of the last increment, carbon dioxide is bubbledthrough the mixture for an additional hour. Thereafter, the reactionmixture is gradually heated to about 146 C. over a 3.25 hour periodwhile blowing with nitrogen to remove water and methanol from themixture. Thereafter, the mixture is permitted to cool to roomtemperature and filtered producing 1,895 grams of the desired overbasedmaterial having a metal ratio of 11.3. The material contains 6.8%mineral oil, 4.18% of the isobutanolamyl alcohol and 30.1% naphtha.

31 EXAMPLE 40 A mixture of 406 grams of naphtha and 214 grams of amylalcohol is placed in a three-liter flask equipped With reflux condenser,gas inlet tubes, and stirrer. The mixture is stirred rapidly Whileheating to 38 C. and adding 27 grams of barium oxide. Then 27 grams ofwater are added slowly and the temperature rises to 45 C. Stirring ismaintained while slowly adding over 0.25 hour 73 grams of oleic acid.The mixture is heated to 95 C. with continued mixing. Heating isdiscontinued and 523 grams of barium oxide are slowly added to themixture. The temperature rises to about 115 C. and the mixture ispermitted to cool to 90 C. whereupon 67 grams of water are slowly addedto the mixture and the temperature rises to 107 C. The mixture is thenheated within the range of 107-120 C. to remove water over a 3.3 hourperiod while bubbling nitrogen through the mass. Subsequently, 427 gramsof oleic acid is added over a 1.3 hour period while maintaining atemperature of 120125 C. Thereafter heating is terminated and 236 gramsof naphtha is added. Carbonation is commenced by bubbling carbon dioxidethrough the mass at two cubic feet per hour for 1.5 hours during whichthe temperature is held at 108-117 C. The mixture is heated under anitrogen purge to remove water. The reaction mixture is filtered twiceproducing a filtrate analyzing as follows: sulfate ash content, 34.42%;metal ratio, 3.3. The filtrate contains 10.7% amyl alcohol and 32%naphtha.

EXAMPLE 41 A reaction mixture comprising 1800 grams of a calciumoverbased petrosulfonic acid containing 21.7% by weight mineral oil,36.14% by weight naphtha, 426 grams naphtha, 255 grams of methanol, and127 grams of an equal molar amount of isobutanol and amyl alcohol areheated to 45 C. under reflux conditions and 148 grams of Mississippilime (commercial calcium hydroxide) is added thereto. The reaction massis then blown with carbon dioxide at the rate of 2 cubic feet per hourand thereafter 148 grams of additional Mississippi lime added.Carbonation is continued for another hour at the same rate. Twoadditional 147 gram increments of Mississippi lime are added to thereaction mixture, each increment followed by about a 1 hour carbonationprocess. Thereafter, the reaction mass is heated to a temperature of 138C. while bubbling nitrogen therethrough to remove water and methanol.After filtration, 2,200 grams of a solution of the barium overbasedpetrosulfonic acid is obtained having a metal ratio of 12.2 andcontaining 12.5% by weight mineral oil, 34.15% by weight naphtha, and4.03% by weight of the isobutanol amyl alcohol mixture.

EXAMPLE 42 (a) Following the procedure of Example 2 above, thecorresponding lead product is prepared by replacing the bariumpetrosulfonate with lead petroleum sulfonate (1 equivalent) and bariumoxide with lead oxide (25 equivalents).

(b) Following the procedure of Example 5(a) above, the correspondingoverbased sodium sulfonate is prepared by replacing the barium oxidewith sodium hydroxide.

The above examples illustrate various means for preparing overbasedmaterials suitable for conversion to the non-Newtonian colloidaldisperse systems utilized in the present invention. Obviously, it iswithin the skill of the art to vary these examples to produce anydesired overbased material. Thus, other acidic materials such asmentioned herein'before can be substituted for the CO S0 and acetic acidused in the above examples. Similarly, other metal bases can be employedin lieu of the metal base used in any given example. Or mixtures ofbases and/or mixtures of materials which can be overbased can beutilized. Similarly, the amount of mineral oil or other non-polar,inert, organic liquid used as the overbasing medium can be varied widelyboth during overbasing and in the overbased product.

The following examples illustrate the conversion of the Newtonianoverbased materials into non-Newtonian colloidal disperse systems byhomogenization with conversion agents.

EXAMPLE I To 733 grams of the overbased material of Example 5 (a) thereis added 179 grams of acetic acid and 275 grams of a mineral oil (havinga viscosity of 2000 SUS at 100 F.) at C. in 1.5 hours with vigorousagitation. The mixture is then homogenized at 150 C. for 2 hours and theresulting material is the desired colloidal disperse system.

EXAMPLE II A mixture of 960 grams of the overbased material of Example5(1)), 256 grams of acetic acid, and 300 grams of a mineral oil (havinga viscosity of 2000 SUS at F.) is homogenized by vigorous stirring at150 C. for 2 hours. The resulting product is a non-Newtonian colloidaldisperse system of the type contemplated for use by the presentinvention.

The overbased materials of Examples I and II can be converted Withoutthe addition of additional mineral oil or if another inert organicliquid is substituted for the mineral oil.

EXAMPLE III A mixture of 150 parts of the overbased material of Example6, 15 parts of methyl alcohol, 10.5 parts of amyl alcohol, and 45 partsof water is heated under reflux conditions at 7174 C. for 13 hourswhereupon the mixture gels. The gel is heated for 6 hours at 144 C.,diluted with 126 parts of the mineral oil of the type used in Example Iabove the diluted mixture heated to 144 C. for an additional 4.5 hours.The resulting thickened product is a colloidal disperse system. Again,it is not necessary that the material be diluted with mineral oil inorder to be useful. The gel itself which results from the initialhomogenization of the overbased material and the lower alkanol mixtureis a particularly useful colloidal disperse system for incorporatinginto resinous compositions.

EXAMPLE IV A mixture of 1000 grams of the product of Example 12, 80grams of methanol, 40 grams of mixed primary amyl alcohols (containingabout 65% by weight of normal amyl alcohol, 3% by weight of isoamylalcohol, and 32% of Z-methyl-l-butyl alcohol) and 80 grams of water areintroduced into a reaction vessel and heated to 70 C. and maintained atthat temperature for 4.2 hours. The overbased material is converted to agelatinous mass, the latter is stirred and heated at 150 C. for a periodof about 2 hours to remove substantially all the alcohols and water. Theresidue is a dark green gel which is a particularly useful colloidaldisperse system.

EXAMPLE V The procedure of Example IV is repeated except that grams ofwater is used to replace the water-alkanol mixture employed as theconversion agent therein. Conversion of the Newtonian overbased materialinto the non-Newtonian colloidal disperse system requires about 5 hoursof homogenization. The disperse system is in the form of a gel.

EXAMPLE VI To 600 parts by weight of the overbased material of Example6, there is added 300 parts of dioctylphthalate, 48 parts of methanol,36 parts of isopropyl alcohol, and 36 parts of water. The mixture isheated to 70-77 C. and maintained at this temperature for 4 hours duringwhich the mixture becomes more viscous. The viscous solution is thenblown with carbon dioxide for 1 hour until substantially neutral tophenolphthalein. The alcohols and water are removed by heating toapproximately 150 C. The residue is the desired colloidal dispersesystem.

EXAMPLE VII To 800 parts of the overbased material of Example 6, thereis added 300 parts of kerosene, 120 parts of an alcoholzwater mixturecomprising 64 parts of methanol, 32 parts of water and 32 parts of theprimary amyl alcohol mixture of Example IV. The mixture is heated to 75C. and maintained at this temperature for 2 hours during which time theviscosity of the mixture increases. The Water and alcohols are removedby heating the mixture to about 150 C. while blowing with nitrogen for 1hour. The residue is the desired colloidal disperse system having theconsistency of a gel.

EXAMPLE VIII A mixture of 340 parts of the product of Example 6, 68parts of an alcoholzwater solution consisting of 27.2 parts of methanol,20.4 parts of isopropyl alcohol and 20.4 parts of water, and 170 partsof heptane is heated to 65 C. During this period, the viscosity of themixture increases from an initial value of 6,250 to 54,000.

The thickened colloidal disperse system is further neutralized byblowing the carbon dioxide at the rate of 5 lbs. per hour for 1 hour.The resulting mass is found to have a neutralization number of 0.87(acid to phenolphthalein indicator).

EXAMPLE IX The procedure of Example VIII is repeated except that thecalcium overbased material of Example 6 is replaced by an equivalentamount of the cadmium and barium overbased material of Example 17.Xylene (200 parts) is used in lieu of the heptane and the furthercarbonation step is omitted.

EXAMPLE X A mixture of 500 parts of the overbased material of Example 6,312 parts of kerosene, 40 parts of methylethyl ketone, 20 parts ofisopropyl alcohol, and 50 parts of water is prepared and heated to 75 C.The mixture is maintained at a temperature of 7075 C. for 5 hours andthen heated to 150 C. to remove the volatile components. The mixture isthereafter blown with ammonia for 30 minutes to remove most of the finaltraces of volatile materials and thereafter permitted to cool to roomtemperature. The residue is a brownish-tan colloidal disperse system inthe form of a gel.

EXAMPLE XI A mixture of 500 parts of the product of Example 6, 312 partsof kerosene, 40 parts of acetone, and 60 parts of water is heated toreflux and maintained at this temperature for 5 hours with stirring. Thetemperature 01f the material is then raised to about 155 C. whileremoving the volatile components. The residue is a viscous gel-likematerial which is the desired colloidal disperse system.

EXAMPLE X111 The procedure of Example XI is repeated with thesubstitution of 312 parts of heptane for the kerosene and 60 parts ofwater for the acetone-water mixture therein. At the completion of thehomogenization, hydrogen gas is bubbled through the gel to facilitatethe removal of water and any other volatile components.

EXAMPLE XI'II To 500 parts of the overbased material of Example 9, thereis added 312 parts of kerosene, 40 parts of o-cresol, and 50 parts ofwater. This mixture is heated to the reflux temperature (70- 75 C.) andmaintained at this temperature for 5 hours. The volatile components arethen removed from the mixture by heating to 150 C. over a period of 2hours. The residue is the desired colloidal disperse system containingabout 16 by weight of kerosene.

EXAMPLE XIV A mixture of 500 parts of the overbased material of Example5(a) and 312 parts of heptane is heated to C. whereupon 149 parts ofglacial acetic acid (99.8% by weight) is added dropwise over a period of5 hours. The mixture is then heated to 150 C. to remove the volatilecomponents. The resulting gel-like material is the desired colloidaldisperse system.

EXAMPLE XV The procedure of Example XIV is repeated except that 232parts of boric acid is used in lieu of the acetic acid. The desired gelis produced.

EXAMPLE XVI The procedure of Example XI'I is repeated except that thewater is replaced by 40 parts of methanol and 4.0 parts of diethylenetriamine. Upon completion of the homogenization, a gel-like colloidaldisperse system is produced.

EXAMPLE XVII A mixture of 500 parts of the product of Example 6 and 300parts of heptane is heated to 80 C. and 68 parts of antharinlic acid isadded over a period of 1 hour while maintaining the reaction temperaturebetween 80 and C. The reaction mixture is then heated to C. over a 2hour period and blown with nitrogen for 15 minutes to remove thevolatile components. The resulting colloidal disperse system is amoderately stiff gel.

EXAMPLE XV I'II The procedure of Example XVI-I is repeated except thatthe anthranilic acid is replaced by 87 parts of adipic acid. Theresulting product is very viscous and is the desired colloidal dispersesystem. This gel can be diluted, if desired, with mineral oil or any ofthe other materials said to be suitable for disperse mediumshereinabove.

EXAMPLE XJX A mixture of 500 parts of the product of Example 8 and 300parts of heptane is heated to 80 C. whereupon 148 parts of glacialacetic acid is added over a period of 1 hour while maintaining thetemperature Within the range of about 80-88 C. The mixture is thenheated to 150 C. to remove the volatile components. The residue is aviscous gel which is useful for incorporation into the polymeric resinsof the present invention. It may also be diluted with a materialsuitable as a disperse medium to facilitate incorporation into resinouscompositions.

EXAMPLE XX A mixture of 300 parts of toluene and 500 parts of anoverbased material prepared according to the procedure of Example 7 andhaving a sulfate ash content of 41.8% is heated to 80 C. whereupon 124parts of glacial acetic acid is added over a period of 1 hour. Themixture is then heated to C. to remove the volatile components. Duringthis heating, the reaction mixture becomes very viscous and 380 parts ofmineral oil is added to facilitate the removal of the volatilecomponents. The resulting colloidal disperse system is a very viscousgrease-like material.

XXI

A mixture of 700 parts of the overbased material of Example 5(b), 70parts Otf water, and 350* parts of toluene is heated to reflux and blownwith carbon dioxide at the rate of 1 cubic foot per hour for 1 hour. Thereaction product is a soft gel.

35 EXAMPLE XXII The procedure of Example XVIII is repeated except thatthe adipic acid is replaced by 450 grams of di(4-methyl-amyl)phosphorodithioic acid. The resulting material is a gel.

EXAMPLE XXHEI The procedure of Example XVI is repeated except that themethanol-amine mixture is replaced by 250 parts of a phosphorus acidobtained by treating with steam at 150 C. the product obtained byreacting 1000 parts of polyisobutene having a molecular weight of about60,000, with 24 parts of phosphorus pentasulfide. The product is avicous brown gel-like colloidal disperse system.

EXAMPLE XXIV The procedure of Example XX is repeated except that theoverbased material therein is replaced by an equivalent amount ofpotassium overbased material of Example 18 and the heptane is replacedby an equivalent amount of toluene.

EXAMPLE XXV The overbased material of Example 6 is isolated as a drypowder by precipitation out of a benzene solution through the additionthereto of acetone. The precipitate is washed with acetone and dried.

A mixture of 45 parts of a toluene solution of the above powder (364parts of toluene added to 500 parts of the powder to produce a solutionhaving a sulfate ash content of 43%), 36 parts of methanol, 27 parts ofwater, and 18 parts of mixed isomeric primary amyl alcohols (describedin Example IV) is heated to a temperature within the range of 7075 C.The mixture is maintained at this temperature for 2.5 hours and thenheated to remove the alkanols. The resulting material is a colloidaldisperse system substantially free from any mineral oil. If desired, thetoluene present in the colloidal disperse system as the disperse mediumcan be removed by first diluting the disperse system with mineral oiland thereafter heating the diluted mixture to a temperature of about 160C. whereupon the toluene is vaporized.

EXAMPLE XXVI Calcium overbased material similar to that prepared inExample 6 is made by substituting xylene for the mineral oil usedtherein. The resulting overbased material has a xylene content of about25% and a sulfate ash content of 39.3%. This overbased material isconverted to a colloidal disperse system by homogenizing 100 parts ofthe overbased material with 8 parts of methanol, 4 parts of the amylalcohol mixture of Example 'IV, and 6 parts of water. The reaction massis mixed for 6 hours while maintaining the temperature at 75 78 C.Thereafter, the disperse system is heated to remove the alkanols andwater. If desired, the gel can be diluted by the addition of mineraloil, toluene, xylene, or any other suitable disperse medium.

EXAMPLE XXV II Air at the rate of cubic feet per hour is blown throughan overbased material of the type prepared according to Example 6 havinga calcium sulfonate ash content of 44.1% while rapidly stirring it at205 C. for 24 hours. The product, on cooling is a gel having a calciumsulfate ash content of 48.14% and a reflux base number of 368.

EXAMPLE XXVIII A colloidal disperse system of the type prepared inExample XXVII is obtained following the same technique and blowing withair for 28 hours at a temperature of 190 C.

36 EXAMPLE XXIX A solution of 1,000 grams of the gel-like colloidal disperse system of Example III is dissolved in 1,000 grams of toluene bycontinuous agitation of these two components for about 3 hours. Amixture of 1000 grams of the resulting solution, 20 grams of Water, and20 grams of methanol are added to a 3-liter flask. Thereafter, 92.5grams of calcium hydroxide is slowly added to the flask with stirring.An exothermic reaction takes place raising the temperature to 32 C. Theentire reaction mass is then heated to about 60 C. over a 0.25 hourperiod. The heated mass is then blown with carbon dioxide at the rate of3 standard cubic feet per hour for 1 hour while maintaining thetemperature at 6070 C. At the conclusion of the carbonation, the mass isheated to about 150 C. over a 0.75 hour period to remove water,methanol, and toluene. The resulting product is a clear, light browncolloidal disperse system in the form of a gel. In this manneradditional metal containing particles are incorporated into thecolloidal disperse system.

At the conclusion of the carbonation step and prior to removing thewater, methanol, and toluene, more calcium hydroxide could have beenadded to the mixture and the carbonation step repeated in order to addstill additional metal-containing particles to the colloidal dispersesystem.

EXAMPLE XXX A mixture of 1200 grams of the gel produced according toExample III, 600 grams of toluene, and 48 grams of water is blown withcarbon dioxide at 2 standard cubic feet per hour while maintaining thetemperature at 55-65 C. for 1 hour. The carbonated reaction mass is thenheated at 150 C. for 1.75 hours to remove the water and toluene. Thisprocedure improves the texture of the colloidal disperse systems andconverts any calcium oxide or calcium hydroxide present in the gelproduced according to Example III into calcium carbonate particles.

EXAMPLE XXXI A mixture comprising 300 grams of water, 70 grams of theamyl alcohol mixture identified in Example IV above, 100 grams ofmethanol, and 1000 grams of a barium overbased oleic acid, preparedaccording to the general technique of Example 3 by substituting oleicacid for the petrosulfonic acid used therein, and having a metal ratioof about 3.5 is thoroughly mixed for about 2.5 hours While maintainingthe temperature within the range of from about 72-74 C. At this pointthe resulting colloidal disperse system was in the form of a very softgel. This material was then heated to about 150 C. for a 2 hour periodto expel methanol, the amyl alcohols, and water. Upon removal of theseliquids, the colloidal disperse system Was a moderately stiff, gel-likematerial.

EXAMPLE XXXII A dark brown colloidal disperse system in the form of avery stiff gel was prepared from the product of Example 40 using amixture of 64 grams of methanol and grams of water as the conversionagent to convert 800 grams of the overbased material. After theconversion process, the resulting disperse system is heated to about 150C. to remove the alcohol and water.

EXAMPLE XXXIII 1000 grams of the overbased material of Example 39 isconverted to a colloidal disperse system by using as a conversion agenta mixture of grams of methanol and 300 grams of water. The mixture isstirred for 7 hours at a temperature within the range of 72-80 C. At theconclusion of the mixing, the resulting mass is heated gradually to atemperature of about C. over a 3 hour period to remove all volatileliquid contained therein. Upon removal of all volatile solvents, a tanpowder was obtained. By thoroughly mixing this tan powder to a suitableorganic liquid such as naphtha, it is again transformed into a colloidaldisperse system.

EXAMPLE XXXIV A mixture of 1000 grams of the product of Example 41, 100grams of water, 80 gram of methanol, and 300 grams of naphtha were mixedand heated to 72 under reflux conditions for about hours. A light brownviscous liquid material is formed which is the desired colloidaldisperse system. This liquid is removed and consists of the colloidaldisperse system wherein about 11.8% of the disperse medium is mineraloil and 88% is naphtha.

Following the techniques of Example III additional overbased materialsas indicated below are converted to the corresponding colloidal dispersesystems.

Overbased material converted Example No. to colloidal disperse systemXXXV Example 15 XXXVI Example 21 XXXV II Example 23 XXXVIII Example24(a) XXXIX Example 28 XL Example 31 XLI Example 39 XLII Example 40 Thepreparation of other non-Newtonian colloidal disperse systems useful inthe compositions of this invention are disclosed in applicants copendingapplications Ser. No, 535,048 filed Mar. 17, 1966, now U.S. 3,372,115,and Ser. No. 535,693 filed Mar. 21, 1966.

The change in rheological properties associated with conversion of anon-Newtonian overbased material into a Newtonian colloidal dispersesystem is demonstrated by the Brookfield viscometer data derived fromoverbased materials and colloidal disperse systems prepared therefrom.In the following samples, the overbased material and the colloidaldisperse systems are prepared according to the above-discussed andexemplified techniques. In each case, after preparation of the overbasedmaterial and the colloidal disperse system, each is blended withdioctylphthalate (DOP) so that the compositions tested in the viscometercontains 33.3% by weight DOP (Samples A, B, and C) or 50% by weight DOP(Sample D). In Samples A-C, the acidic material used in preparing theoverbased material is carbon dioxide while in Sample D, acetic acid isused. The samples each are identified by two numbers, (1) and (2). Thefirst is the overbased materialDOP composition and the second thecolloidal disperse-systemDOP composition. The overbased materials of thesamples are further characterized as follows:

Sample A Calcium overbased petrosulfonic acid having a metal ratio ofabout 12.2.

is tabulated below. The data of all samples is collected at 25 C.

representative preferred acidic esters of phosphoric acids suitable forpreparing the reaction products of this invention.

Example (1) Apolyisobutene-substituted phenol is prepared by mixing 940parts (by weight) of phenol and 2200 parts of polyisobutene having amolecular weight of 350 at 50- 55 C. in the presence of 30 parts ofboron trifiuoride. The unused phenol and other volatile substances areremoved by heating the alkylated phenol to 220 C./ 12 mm. The resultingalkylated phenol has a hydroxyl content of 3.7%. A mixture of 490 partsof this alkylated phenol, 50 parts of phosphorus pentoxide, and 180parts of xylene (molar ratio of the phenol to phosphorus pentoxide being3:1) is prepared at 3850 C. and thereafter heated at -85 C. for 4 hours.The resulting mixture is filtered and the filtrate is a xylene solutionof the acidic, phosphorus-containing composition having a phosphoruscontent of 3.1% and a neutralization number of 76 acid.

Example (2) An acidic phosphorus-containing composition is preparedaccording to the procedure of Example (1) except that the polyisobutenesubstituent of the phenol reactant has a molecular weight of 1000.

Example (3) An acidic, phosphorus-containing composition is preparedaccording to the procedure of Example (1) except that the phenolreactant is a polypropene-substituted phenol wherein the polypropenesubstituent has a molecular weight of 2000.

Example (4) Para-tertiary amylphenol (1900 parts, 11.6 moles) is meltedby heating to 295 C. whereupon 440 parts (3.1 moles) of phosphoruspentoxide is added in 1 hour while maintaining the temperature between-100 C. The mixture is then heated to C. in 5 hours and maintained atthis temperature for an additional 5 hours. The mixture is cooled to 95C. and 585 parts of isobutyl alcohol is added. The mixture is stirredfor 30 minutes. The solution is the desired product having a phosphoruscontent of 6.61%, and a neutralization number (phenolphthalein) of 183acid.

Example (5) A mixture of 286 parts (2 moles) of allyl phenol and 328parts (2 moles) of para-tertiary amyl phenol is heated to 155165 C. and142 parts (1 mole) of phosphorus pentoxide is added over a period of 1hour. The reaction mixture is heated at -170 C. for 6 hours. The residueis the desired product having a phosphorus content of 8.04% and aneutralization number (phenolphthalein) of 224 acid.

Example (6 Para-tertiary amylphenol (492 parts, 3 moles) is melted byheating to 90 C. whereupon 213 parts (1.5 moles) of phosphorus pentoxideis added in 20 minutes and the reaction temperature is raised to 160 C.The mixture is then heated to 185 C. and maintained at this temperaturefor a total of 7 hours. The residue is the desired product having aphosphorus content of 12.8% and a neutralization number(phenolphthalein) of 351. acid.

the para-tertiary amylphenol is replaced on a molar basis withpara-dodecylphenol.

Example (8 A mixture of 1412 parts (1.2 moles) of a 1:1 (molar)copolymer of allyl alcohol and styrene having an average molecularweight of 1100, 168 parts (1 mole) of paratert-amyl phenol, 68 parts(0.5 mole) of phosphorus pentoxide and 1648 parts of xylene is preparedat room temperature and then heated at reflux for 6 hours. The reactionis stirred throughout the period. At the end of this time the xylene isremoved by distillation to yield a plastic, non-viscous mass. Theresidue, While still hot, i.e., about 100 C., is diluted with 824 gramsof isobutyl alcohol to give a 65% solution of the desired phosphoruscomposition having a phosphor-us content of 1.16% and a neutralizationnumber (phenolphthalein) of 22.6 acid.

Example (9) A polyisobutene-substitued phenol is prepared by mixing 940parts of phenol and 2200 parts of polyisobutene having a molceularweight of 350 at 50-55 C. in the presence of 30 parts of borontrifluoride, and distilling off the unused phenol and other volatilesubstances by heating the alkylated phenol to 220 C./ 12 mm. Theresulting alkylated phenol has a hydroxyl content of 3.7%.

A mixture of 1089 parts of xylene and 524 parts of the above preparedpolyisobutene-substituted phenol is heated to 50 C. whereupon 523 partsof 1:1 (molar) copolymer of allyl alcohol and styrene having an averagemolecular weight of 1100 is added over a period of 20 minutes at 50 C.Solution was complete after 1 hour at this temperature. Phosphoricanhydride (52 parts) is added over a period of 15 minutes at 50 C. andthe mixture is heated to the boiling point and to 145 C. in 1.2 hours.The mixture is stirred and maintained at this temperature while removingwater-xylene azeotrope over a period of 6 hours. The residue is cooledto 40 C. The residue, a 50% solution in xylene, has a phosphorus contentof 1.03% and a neutralization number (bromophenol blue) of acid.

Example (10) A mixture of 800 parts (0.73 mole) of the copolymerdescribed in Example 8, 272 parts (1.66 moles) of para-tertiary amylphenol, 80 parts (0.57 mole) of phosphorus pentoxide, and 1148 parts ofxylene is prepared and heated at reflux tempertaure (132-140 C.) for 6hours while the water of the reaction is removed by means of a side-armwater trap. The pressure in the reaction vessel is then lowered to 30mm. Hg to remove the xylene salt. After all of the xylene has beenremoved, 616 parts of isobutyl alcohol is added. The resulting product,a 65% solution of the desired acidic phosphorus-containing compositionin isobutyl alcohol, has a phosphorus content of 2.0%.

Example (11) A mixture of 313 parts (0.284 mole) of the copolymerdescribed in Example (8), 314 parts (0.786 mole) ofmono-(polyisobutene-substituted phenol wherein the polyisobutenesubstituent contatins an average of about 22 carbon atoms, 31 parts(0.218 mole) of phosphorus pentoxide, and 660 parts of xylene is heatedto the reflux temperature (ca. 140 C.) and maintained at thistemperature for 6 hours while water is removed by means of a side-armwater trap. Substantially all the xylene is removed by distillation ofthe mass at 140 C./20 mm. and then the residue is diluted with 350 partsof isobutyl alcohol. The product, a 65 solution of the acidicphosphorus-containing composition in isobutyl alcohol is found to have aphosphorus content of 1.35% and a neutralization number of 16.7.

Additional examples of the acidic phosphorus-contain- 40 ingcompositions of this invention are shown in Table II. They are preparedin the same manner set forth in Example (8) using the indicatedquantities of reagents.

TABLE II.-MOLES OF THE INDICATED STARTING MATERIALS TO BE EMPLOYEDExample Oopoly- Alkylphenol Phosphorus No. mer 1 identity Amountpentoxide 0.87 Para-tert amylphenol- 16.2 4

5 Heptylphenol 12 4 5 Para-cresol 12 4 5 Nonyl phenol 12 4 1 Asdescribed in Example (8) As mentioned previously, the compositions ofthis invent-ion are obtained by the reaction of the disperse systemswith the acidic esters of phosphoric acids. Generally, from 5 to 10parts by weight of the disperse system is reacted with from about 1 to 2parts by weight of the acidic phosphorous-containing composition. Thepreferred ratio is from about 7 parts by weight of the greasecomposition to 1 part by weight of the acidic phosphorous-containingcomposition. The reaction is effected simply by mixing the two reactantsat a temperature between about 25 C. and C. although in some instances,the temperature may be 150 C. or higher. The reaction is preferablycarried out in the presence of a hydrocarbon or halo hydrocarbon solventwhich facilitates temperature control and mixing of the reactants.Examples of such solvents include the alkanes having from five tofifteen carbon atoms, the aromatic hydrocarbons having from six tothirty carbon atoms, the various petroleum distillates and the halo andpolyhalo hydrocarbons having from two to twenty carbon atoms. Morespecifically, examples of such solvents include nhexane, n-pentane,iso-octane, dodecane, benzene, xylene, aromatic petroleum spirits,mineral spirits, turpentine, 1,1,l-trichloroethane, 1,1-dichlorobutane,1,4-dichlorobutane, l-chlorohexane, and chlorocyclohexane. In general,the grease composition is dissolved in the solvent (at the refluxtemperature if necessary), and the acidic phosphorous-containingcomposition is then added to the solution.

The chemical constitution of the product of this reaction is notprecisely known. The reaction is, however, exothermic, and carbondioxide is formed during the reaction as evidenced by its evolution.

A particularly useful corrosion inhibiting composition is obtained whencommercial resins are added to the reaction product. Resins which havebeen found useful are the hydrocarbon resins having a softening point ofat least 100 C., and preferably having a softening point range of fromabout 100 to C. The addition of such resins results in a coatingcomposition which is firm rather than soft and greasy. Thischaracteristic of the rust inhibiting compositions is desired because itprov-ides additional resistance to abrasion, dirt pickup, gravel pickup,etc. Firmness of the coating is desired where the metal parts containingsuch a coating are to be used in areas frequented by humans and animals.Soft grease-life coatings can be easily removed by humans and animalscoming in contact with the metal parts. In this way, messy dark depositsare transferred from the metal parts to the human or animal bodies.Additionally, the soft grease-like coatings which have been transferredto the animals body may then be transferred to various household itemssuch as sofas, carpets, draperies, etc. It is thus obvious that from aconsumers standpoint alone, a firm, non-grease-like coating isdesirable.

Examples of the hydrocarbon resins which have been found useful in thecompositions of this invention include coumaroneindenes, polystyrenes,polymerized beta-pinenes, and higher molecular weight polyisobutenes.Obviously, the resins chosen to be added to a particular compositionshould be miscible with the composition

